![Page 1: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/1.jpg)
1
Supporting Information
Table of Contents
I. General procedures ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙2
II. General procedures for preparation of starting materials∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙2
i. General procedures for preparation of starting materials 1a~1f, 1h~1i, 1m~1w ∙∙∙∙∙∙∙∙∙∙∙∙2
ii. General procedures for preparation of starting materials 1j~1l and 1x~y∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙2
iii. General procedures for preparation of starting material 1g ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙3
iv. General procedures for preparation of starting materials 1z~1ag∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙3
III. Characterization data of starting materials ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙3
IV. UV-vis absorption spectra of 1a ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙15
V. General procedures for heteroaryl/aryl rearrangement ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙16
i. General procedures for heteroaryl rearrangement ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙16
ii. General procedures for aryl rearrangement ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙16
VI. Characterization data of rearrangement products ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙16
VII. References ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙29
VIII. Copies of the 1H, 19F and 13C NMR spectra ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙30
Electronic Supplementary Material (ESI) for Chemical Science.This journal is © The Royal Society of Chemistry 2020
![Page 2: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/2.jpg)
2
I. General procedures
All reagents and solvents were purchased from commercial sources and used without further purification unless otherwise stated. All reactions were monitored by thin-layer chromatography (TLC). All reactions were carried out in argon atmosphere unless otherwise stated. Column chromatography was performed on silica gel (200-300 mesh) and visualized with ultraviolet light. Ethyl acetate and petroleum ether were used as eluents. 1H, 13C and 19F spectra were recorded at room temperature on a Varian Mercury plus 300 or Bruker AV400 or Agilent INOVA 600 MHz with TMS as an internal standard and CDCl3 as solvent. Fourier transform infrared spectra (FT-IR) were recorded on Agilent Technologies Cary 630 instrument or Bruker TENSOR 27 instrument. HRMS analyses were made by Lanzhou University by means of ESI. Melting points were measured on micro melting point apparatus and uncorrected.
II. General procedures for preparation of starting materials
i. General procedures for preparation of starting materials 1a~1f, 1h~1i, 1m~1w
Starting materials 1a~1f, 1h~1i, 1m~1z were synthesized according to the literature procedures[1]. Salicylaldehyde (1.17 g, 9.6 mmol, 1.2 equiv.), 2-bromopyridine (1.26 g, 8.0 mmol, 1.0 equiv.), CuI (76.2 mg, 0.4 mmol, 0.05 equiv.), picolinic acid (98.5 mg, 0.8 mmol, 0.1 equiv.) and K3PO4 (3.4 g, 16 mmol, 2.0 equiv.) in 16 mL dry DMSO were heated at 80 °C for 24 h under argon. The reaction mixture was cooled to room temperature, 16 mL H2O was added and extracted with 3 × 50 mL EtOAc. The combined organic phases were washed with brine, dried over anhydrous
MgSO4 and concentrated under reduced pressure. Purification by column chromatography on silica (PE/EA = 16/1) affords 1a.
ii. General procedures for preparation of starting materials 1j~1l and 1x~y
Starting materials 1j~1l and 1x~y were synthesized according to the literature procedures[2]. Salicylaldehyde (977 mg, 8.0 mmol, 1.0 equiv.), 2-chloro-5-(trifluoromethyl) pyridine (1.45 g, 8.0 mmol, 1.0 equiv.) and K2CO3 (1.11 g, 8.0 mmol, 1.0 equiv.) in 16 mL dry DMF were heated at 150 °C for 5 h under argon. The reaction mixture was cooled to room temperature, 16 mL H2O was added and extracted with 3 × 40 mL EtOAc. The combined organic phases were washed with brine, dried over anhydrous MgSO4 and concentrated under reduced pressure. Purification by column chromatography on silica (PE/EA = 25/1) affords 1j.
![Page 3: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/3.jpg)
3
iii. General procedures for preparation of starting material 1g
Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde (1.78 g, 9.6 mmol, 1.2 equiv.), 5-fluoropyridin-2-ol (0.9 g, 8.0 mmol, 1.0 equiv.), CuI (76.2 mg, 0.4 mmol, 0.05 equiv.), picolinic acid (98.5 mg, 0.8 mmol, 0.1 equiv.) and K3PO4 (3.4 g, 16 mmol, 2.0 equiv.) in 16 mL dry DMSO were heated at 80 °C for 24 h under argon. The reaction mixture was cooled to room temperature, 16 mL H2O was added and extracted with 3 × 50 mL EtOAc. The combined organic phases were washed with brine, dried over anhydrous MgSO4 and concentrated under reduced pressure. Purification by column chromatography on silica (PE/EA = 20/1) affords 1g.
iv. General procedures for preparation of starting materials 1z~1ag
Starting materials 1z~1ag were synthesized according to the literature procedures[2]. To a DMA (16 mL) solution containing 2-fluorobenzaldehydes (0.85 mL, 8.0 mmol, 1.0 equiv.) and 4-hydroxybenzonitrile (954 mg, 8.0 mmol, 1.0 equiv.) were added K2CO3 (1.10 g, 8.0 mmol, 1.0 equiv.), and the reaction mixture was stirred for 3
h at 170 °C under argon atmosphere. The reaction mixture was cooled to room
temperature, diluted with H2O (16 mL), extracted with EtOAc (40 mL x 3), and the
organic layer was washed with brine, dried with anhydrous MgSO4 and concentrated under reduced pressure. Purification by column chromatography on silica (PE/EA = 25/1) affords 1z.
III. Characterization data of starting materials
O
O
N
2-(Pyridin-2-yloxy)benzaldehyde (1a) Light yellow solid, 1.37 g, 86%.1H NMR (300 MHz, CDCl3) δ 10.31 (s, 1H), 8.18 (d, J = 3.4 Hz, 1H), 7.98 (dd, J = 7.8, 1.6 Hz, 1H), 7.77 (td, J = 7.9, 2.0 Hz, 1H), 7.69 – 7.60 (m, 1H), 7.34 (t, J = 7.6 Hz, 1H), 7.18 (d, J = 8.3 Hz, 1H), 7.10 – 7.03 (m, 2H).13C NMR (75 MHz, CDCl3) δ 189.3, 163.5, 156.6, 147.9, 140.1, 135.7, 128.8, 128.6, 125.3, 122.6, 119.4, 112.0; 1H and 13C NMR data agreed with the literature [3].
O
O
N
Me
![Page 4: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/4.jpg)
4
2-((3-Methylpyridin-2-yl)oxy)benzaldehyde (1b)Colorless oil, 0.94 g, 55%1H NMR (300 MHz, CDCl3) δ 10.30 (d, J = 0.6 Hz, 1H), 8.01 – 7.93 (m, 2H), 7.66 – 7.55 (m, 2H), 7.31 (t, J = 7.3 Hz, 1H), 7.16 (d, J = 8.2 Hz, 1H), 7.01 – 6.93 (m, 1H), 2.41 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.4, 161.8, 156.9, 144.9, 140.4, 135.6, 128.7, 128.4, 125.0, 122.6, 121.9, 119.5, 16.1.IR (KBr, ν / cm-1): 2999, 2855, 2753, 1692, 1650, 1602, 1578, 1479, 1449, 1415, 1274, 1237, 1188, 1114, 1095, 990, 892, 833, 792, 750.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0863.
O
O
N
Me
2-((4-Methylpyridin-2-yl)oxy)benzaldehyde (1c)Colorless oil, 1.16 g, 68%.1H NMR (300 MHz, CDCl3) δ 10.31 (d, J = 0.5 Hz, 1H), 8.00 (dd, J = 20.1, 6.2 Hz, 2H), 7.62 (t, J = 7.2 Hz, 1H), 7.31 (t, J = 7.5 Hz, 1H), 7.15 (d, J = 8.3 Hz, 1H), 6.88 (d, J = 6.6 Hz, 2H), 2.39 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.4, 163.8, 156.8, 151.8, 147.4, 135.7, 128.7, 128.5, 125.1, 122.5, 120.8, 112.2, 21.2.IR (KBr, ν / cm-1): 3008, 2856, 2757, 1693, 1603, 1562, 1478, 1455, 1394, 1288, 1273, 1215, 1149, 1096, 947, 840, 792, 752, 631.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0862.
O
O
NMe
2-((5-Methylpyridin-2-yl)oxy)benzaldehyde (1d)Colorless oil, 1.28 g, 75%.1H NMR (300 MHz, CDCl3) δ 10.34 (s, 1H), 7.98 (ddd, J = 9.5, 4.8, 1.2 Hz, 2H), 7.67 – 7.54 (m, 2H), 7.37 – 7.25 (m, 1H), 7.13 (d, J = 8.3 Hz, 1H), 6.96 (d, J = 8.3 Hz, 1H), 2.30 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.5, 161.65, 157.2, 147.6, 140.9, 135.7, 128.9, 128.7, 128.5, 125.0, 122.1, 111.6, 17.7.IR (KBr, ν / cm-1): 2996, 2864, 2757, 1692, 1602, 1580, 1473, 1455, 1377, 1274, 1240, 1154, 1096, 890, 832, 787, 749.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0869.
![Page 5: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/5.jpg)
5
O
O
NOMe
2-((5-Methoxypyridin-2-yl)oxy)benzaldehyde (1e)Colorless oil, 1.47 g, 80%.1H NMR (300 MHz, CDCl3) δ 10.38 (s, 1H), 7.95 (d, J = 7.6 Hz, 1H), 7.85 (d, J = 2.6 Hz, 1H), 7.59 (t, J = 7.7 Hz, 1H), 7.41 – 7.23 (m, 2H), 7.04 (dd, J = 19.7, 8.5 Hz, 2H), 3.84 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.2, 157.4, 156.8, 152.6, 135.4, 132.6, 128.3, 127.8, 126.3, 124.3, 121.0, 112.5, 55.9.IR (KBr, ν / cm-1): 3002, 2865, 2757, 1698, 1600, 1577, 1488, 1451, 1402, 1318, 1273, 1225, 1173, 1090, 955, 821, 792, 755.HRMS (ESI): calcd. for C13H12NO3 ([M+H]+ ): 230.0812, found: 230.0814.
O
O
N
OMe
2-((6-Methoxypyridin-2-yl)oxy)benzaldehyde (1f)Colorless oil, 0.95 g, 52%.1H NMR (300 MHz, CDCl3) δ 10.34 (d, J = 0.7 Hz, 1H), 7.96 (dd, J = 7.8, 1.8 Hz, 1H), 7.64 – 7.59 (m, 2H), 7.31 (t, J = 7.5 Hz, 1H), 7.19 (dd, J = 8.2, 0.6 Hz, 1H), 6.51 – 6.48 (m, 2H), 3.69 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.5, 163.4, 162.0, 156.8, 142.0, 135.5, 128.8, 128.3, 125.1, 122.5, 105.2, 102.2, 53.7.IR (KBr, ν / cm-1): 2987, 2858, 2757, 1694, 1604, 1574, 1473, 1428, 1318, 1275, 1231, 1187, 1143, 1097, 1035, 974, 850, 789, 732.HRMS (ESI): calcd. for C13H12NO3 ([M+H]+ ): 230.0812, found: 230.0813.
O
O
NF
2-((5-Fluoropyridin-2-yl)oxy)benzaldehyde (1g)Light yellow oil, 1.23 g, 71%.1H NMR (300 MHz, CDCl3) δ 10.30 (s, 1H), 8.01 – 7.93 (m, 2H), 7.70 – 7.59 (m, 1H), 7.52 (ddd, J = 9.0, 7.3, 3.1 Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.14 (d, J = 8.3 Hz, 1H), 7.07 (dd, J = 9.0, 3.5 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 189.2, 155.8 (d, J = 119.6 Hz), 146.4, 135.8, 134.8 (d, J = 26.6 Hz), 132.8, 129.1, 128.5, 127.7 (d, J = 21.2 Hz), 125.5, 122.4, 112.9 (d, J = 4.8
![Page 6: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/6.jpg)
6
Hz).19F NMR (376 MHz, CDCl3) δ -134.8 (s).IR (KBr, ν / cm-1): 3016, 2861, 1692, 1602, 1471, 1456, 1385, 1225, 1155, 1096, 1060, 895, 838, 812, 793, 752.HRMS (ESI): calcd. for C12H9FNO2 ([M+H]+ ): 218.0612, found: 218.0615.
O
O
NCl
2-((5-Chloropyridin-2-yl)oxy)benzaldehyde (1h)Colorless oil, 1.16 g, 62%.1H NMR (300 MHz, CDCl3) δ 10.26 (d, J = 0.5 Hz, 1H), 8.09 (dd, J = 2.6, 0.5 Hz, 1H), 7.97 (dd, J = 7.8, 1.5 Hz, 1H), 7.76 – 7.69 (m, 1H), 7.65 (td, J = 8.2, 1.8 Hz, 1H), 7.36 (t, J = 7.4 Hz, 1H), 7.17 (dd, J = 8.2, 0.4 Hz, 1H), 7.04 (dd, J = 8.7, 0.5 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 188.1, 160.9, 155.0, 145.2, 138.9, 134.8, 128.3, 127.6, 125.8, 124.7, 121.7, 111.9.IR (KBr, ν / cm-1): 3034, 2860, 1692, 1603, 1558, 1454, 1396, 1371, 1241, 1209, 1155, 1110, 1062, 889, 829, 805, 766.HRMS (ESI): calcd. for C12H9ClNO2 ([M+H]+ ): 234.0316, found: 234.0318.
O
O
NBr
2-((5-bromopyridin-2-yl)oxy)benzaldehyde (1i)Light yellow oil, 1.11 g, 50%.1H NMR (300 MHz, CDCl3) δ 10.25 (s, 1H), 8.18 (d, J = 2.5 Hz, 1H), 7.96 (dd, J = 7.8, 1.6 Hz, 1H), 7.86 – 7.82 (m, 1H), 7.64 (ddd, J = 8.1, 7.5, 1.8 Hz, 1H), 7.35 (t, J = 7.6 Hz, 1H), 7.16 (dd, J = 8.2, 0.5 Hz, 1H), 6.99 (dd, J = 8.7, 0.5 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 189.0, 162.4, 155.9, 148.5, 142.6, 135.7, 129.3, 128.7, 125.7, 122.7, 114.6, 113.5.IR (KBr, ν / cm-1): 3078, 2858, 1692, 1603, 1574, 1452, 1396, 1364, 1272, 1239, 1211, 1186, 1155, 1089, 1003, 888, 827, 804, 763, 638.HRMS (ESI): calcd. for C12H9BrNO2 ([M+H]+ ): 277.9811, found: 277.9811.
O
O
NCF3
2-((4-(Trifluoromethyl)pyridin-2-yl)oxy)benzaldehyde (1j)Colorless oil, 0.98 g, 46%.
![Page 7: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/7.jpg)
7
1H NMR (300 MHz, CDCl3) δ 10.20 (s, 1H), 8.40 (dd, J = 1.6, 0.9 Hz, 1H), 7.99 (dt, J = 4.7, 2.1 Hz, 2H), 7.73 – 7.65 (m, 1H), 7.42 (t, J = 7.6 Hz, 1H), 7.24 – 7.16 (m, 2H).13C NMR (151 MHz, CDCl3) δ 188.8, 165.7, 155.1, 145.6 (d, J = 4.3 Hz), 136.6 (d, J = 235.1 Hz), 129.8, 128.8, 126.3, 124.4 (d, J = 37.3 Hz), 123.2, 122.8, 122.4 (d, J = 33.8 Hz), 111.8.19F NMR (376 MHz, CDCl3) δ -61.7 (s).IR (KBr, ν / cm-1): 2996, 2865, 1696, 1606, 1478, 1456, 1393, 1328, 1281, 1254, 1210, 1162, 1126, 1077, 1013, 893, 837, 807, 780, 758.HRMS (ESI): calcd. for C13H9F3NO2 ([M+H]+ ): 268.0580, found: 268.0580.
O
O S
N
2-(Benzo[d]thiazol-2-yloxy)benzaldehyde (1k)Orange solid, 1.67 g, 82%.1H NMR (300 MHz, CDCl3) δ 10.37 (d, J = 0.7 Hz, 1H), 8.01 (dd, J = 7.7, 1.8 Hz, 1H), 7.73 – 7.68 (m, 3H), 7.51 – 7.37 (m, 3H), 7.31 (td, J = 7.7, 1.3 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 188.0, 171.2, 156.1, 148.5, 135.8, 132.3, 129.2, 127.6, 126.6, 126.4, 124.5, 121.9 (d, J = 2.3 Hz), 121.4; 1H and 13C NMR data agreed with literature[4].
O
ON
N
Me
Me
2-((3,6-Dimethylpyrazin-2-yl)oxy)benzaldehyde (1l)Yellow solid, M.p. 66 – 67 ℃, 1.32 g, 72%. 1H NMR (300 MHz, CDCl3) δ 10.25 (d, J = 0.7 Hz, 1H), 8.07 (s, 1H), 7.97 (dd, J = 7.8, 1.8 Hz, 1H), 7.63 (ddd, J = 8.3, 7.4, 1.8 Hz, 1H), 7.43 – 7.30 (m, 1H), 7.16 (dd, J = 8.3, 1.0 Hz, 1H), 2.64 (s, 3H), 2.30 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 189.1, 157.3, 155.9, 148.7, 141.4, 138.0, 135.5, 129.2, 128.5, 125.4, 122.6, 20.7, 19.0.IR (KBr, ν / cm-1): 2935, 2858, 1694, 1603, 1540, 1457, 1361, 1281, 1214, 1189, 1158, 1095, 1023, 1006, 883, 851, 810, 759.HRMS (ESI): calcd. for C13H13N2O2 ([M+H]+ ): 229.0972, found: 229.0970.
O
O
N
Me
![Page 8: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/8.jpg)
8
4-Methyl-2-(pyridin-2-yloxy)benzaldehyde (1m)Light yellow oil, 1.52 g, 89%.1H NMR (300 MHz, CDCl3) δ 10.23 (d, J = 0.6 Hz, 1H), 8.18 (dd, J = 5.3, 2.0 Hz, 1H), 7.87 (d, J = 7.9 Hz, 1H), 7.75 (ddd, J = 8.1, 4.9, 2.0 Hz, 1H), 7.13 (dd, J = 8.0, 0.7 Hz, 1H), 7.08 – 7.02 (m, 2H), 6.97 (d, J = 0.4 Hz, 1H), 2.41 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.0, 163.6, 156.5, 147.8, 147.3, 140.0, 128.7, 126.4, 126.2, 122.9, 119.2, 111.9, 22.1.IR (KBr, ν / cm-1): 3011, 2856, 1689, 1612, 1571, 1496, 1467, 1429, 1239, 1144, 1106, 991, 949, 883, 846, 818, 805, 779, 736, 712.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0870.
O
O
N
Me
3-Methyl-2-(pyridin-2-yloxy)benzaldehyde (1n)White solid, M.p. 67 – 68 ℃, 1.23 g, 72%.1H NMR (300 MHz, CDCl3) δ 10.15 (d, J = 0.7 Hz, 1H), 8.09 (ddd, J = 5.0, 2.0, 0.8 Hz, 1H), 7.82 (ddd, J = 7.7, 1.7, 0.5 Hz, 1H), 7.74 (ddd, J = 8.3, 7.2, 2.0 Hz, 1H), 7.54 (ddd, J = 7.5, 1.7, 0.8 Hz, 1H), 7.30 (t, J = 7.7 Hz, 1H), 7.05 – 6.97 (m, 2H), 2.17 (s, 3H).13C NMR (75 MHz, CDCl3) δ 190.0, 163.8, 154.4, 147.9, 140.1, 137.6, 132.9, 129.6, 126.7, 126.0, 118.8, 110.7, 16.4.IR (KBr, ν / cm-1): 3063, 2861, 1698, 1684, 1587, 1464, 1428, 1392, 1241, 1186, 1142, 1084, 922, 880, 817, 777, 736.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0862.
O
O
N
OMe
3-Methoxy-2-(pyridin-2-yloxy)benzaldehyde (1o)White solid, M.p. 101 – 102 ℃, 1.15 g, 63%.1H NMR (300 MHz, CDCl3) δ 10.24 (d, J = 0.6 Hz, 1H), 8.09 (dd, J = 5.0, 2.0 Hz, 1H), 7.73 (ddd, J = 8.3, 7.2, 2.0 Hz, 1H), 7.56 (dd, J = 7.7, 1.6 Hz, 1H), 7.33 (t, J = 7.9 Hz, 1H), 7.24 (dd, J = 8.1, 1.6 Hz, 1H), 7.07 (d, J = 8.3 Hz, 1H), 7.00 (ddd, J = 7.2, 5.0, 0.8 Hz, 1H), 3.77 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.7, 163.8, 152.5, 147.6, 145.5, 139.8, 130.3, 126.2,
![Page 9: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/9.jpg)
9
119.6, 118.8, 118.2, 110.7, 56.4.IR (KBr, ν / cm-1): 2995, 2867, 1687, 1673, 1596, 1568, 1467, 1427, 1400, 1317, 1181, 1143, 1063, 991, 911, 878, 817, 779, 740.HRMS (ESI): calcd. for C13H12NO3 ([M+H]+ ): 230.0812, found: 230.0818.
O
O
NBr
5-bromo-2-(pyridin-2-yloxy)benzaldehyde (1p)White solid, M.p. 54 – 55 ℃, 1.49 g, 67%.1H NMR (300 MHz, CDCl3) δ 10.21 (s, 1H), 8.15 (dd, J = 5.4, 2.0 Hz, 1H), 8.06 (d, J = 2.6 Hz, 1H), 7.80 – 7.75 (m, 1H), 7.71 (dd, J = 8.7, 2.6 Hz, 1H), 7.11 – 7.06 (m, 3H).13C NMR (75 MHz, CDCl3) δ 187.9, 163.2, 155.5, 147.8, 140.2, 138.2, 131.4, 130.0, 124.7, 119.7, 118.6, 112.0.IR (KBr, ν / cm-1): 2996, 2856, 1689, 1590, 1572, 1464, 1428, 1388, 1240, 1178, 1143, 1110, 1058, 992, 893, 864, 837, 774.HRMS (ESI): calcd. for C12H9BrNO2 ([M+H]+ ): 277.9811, found: 277.9812.
O
O
NF
5-Fluoro-2-(pyridin-2-yloxy)benzaldehyde (1q)White solid, M.p. 59 – 60 ℃, 0.88 g, 51%.1H NMR (300 MHz, CDCl3) δ 10.21 (d, J = 3.0 Hz, 1H), 8.16 – 8.13 (m, 1H), 7.77 (ddd, J = 8.3, 7.3, 2.0 Hz, 1H), 7.63 (dd, J = 8.2, 3.2 Hz, 1H), 7.34 (ddd, J = 8.9, 7.5, 3.2 Hz, 1H), 7.19 (dd, J = 9.0, 4.3 Hz, 1H), 7.09 – 7.04 (m, 2H).13C NMR (75 MHz, CDCl3) δ 188.2, 163.5, 159.7 (d, J = 246.3 Hz), 152.4 (d, J = 2.5 Hz), 147.7, 140.2, 129.9 (d, J = 6.5 Hz), 124.8 (d, J = 7.7 Hz), 122.7 (d, J = 24.1 Hz), 119.5, 114.3 (d, J = 23.8 Hz), 111.7.19F NMR (376 MHz, CDCl3) δ -116.1 (s).IR (KBr, ν / cm-1): 3068, 2865, 1692, 1594, 1594, 1487, 1466, 1428, 1396, 1245, 1183, 1141, 1099, 1057, 992, 965, 877, 838, 776, 734, 710.HRMS (ESI): calcd. for C12H9FNO2 ([M+H]+ ): 218.0612, found: 218.0613.
O
O
NCl
5-Chloro-2-(pyridin-2-yloxy)benzaldehyde (1r)Light yellow solid, M.p. 52 – 53 ℃, 1.06 g, 57%.
![Page 10: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/10.jpg)
10
1H NMR (300 MHz, CDCl3) δ 10.23 (d, J = 0.6 Hz, 1H), 8.20 – 8.09 (m, 1H), 7.91 (d, J = 2.7 Hz, 1H), 7.81 – 7.73 (m, 1H), 7.57 (ddd, J = 8.7, 2.7, 0.6 Hz, 1H), 7.16 (d, J = 8.7 Hz, 1H), 7.11 – 7.04 (m, 2H).13C NMR (75 MHz, CDCl3) δ 187.9, 163.2, 154.9, 147.8, 140.2, 135.3, 131.1, 129.7, 128.3, 124.4, 119.7, 112.0.IR (KBr, ν / cm-1): 2995, 2866, 1691, 1594, 1464, 1429, 1389, 1242, 1179, 1111, 1058, 992, 870, 839, 774, 736.HRMS (ESI): calcd. for C12H9ClNO2 ([M+H]+ ): 234.0316, found: 234.0319.
O
O
N
Me
OMe
2-((5-Methoxypyridin-2-yl)oxy)-3-methylbenzaldehyde (1s)Colorless oil, 1.65 g, 85%.1H NMR (300 MHz, CDCl3) δ 10.17 (d, J = 0.7 Hz, 1H), 7.81 (dd, J = 7.7, 1.7 Hz, 1H), 7.73 (d, J = 3.1 Hz, 1H), 7.53 (ddd, J = 7.5, 1.7, 0.8 Hz, 1H), 7.36 – 7.23 (m, 2H), 6.96 (dd, J = 8.9, 0.5 Hz, 1H), 3.80 (s, 3H), 2.16 (s, 3H).13C NMR (75 MHz, CDCl3) δ 190.0, 158.1, 154.8, 152.3, 137.5, 132.9, 132.3, 129.7, 127.2, 126.5, 125.8, 110.8, 56.3, 16.3.IR (KBr, ν / cm-1): 2938, 2839, 1681, 1586, 1484, 1465, 1440, 1384, 1233, 1185, 1084, 1031, 1010, 922, 886, 831, 786, 769, 736, 716.HRMS (ESI): calcd. for C14H14NO3 ([M+H]+ ): 244.0968, found: 244.0974.
O
O
N
Me
Me
3-Methyl-2-((5-methylpyridin-2-yl)oxy)benzaldehyde (1t)
Colorless oil, 1.40 g, 77%.1H NMR (300 MHz, CDCl3) δ 10.15 (s, 1H), 7.89 (d, J = 0.9 Hz, 1H), 7.81 (d, J = 7.8 Hz, 1H), 7.53 (d, J = 8.3 Hz, 2H), 7.31 – 7.26 (m, 1H), 6.92 (d, J = 8.4 Hz, 1H), 2.26 (s, 3H), 2.16 (s, 3H).13C NMR (75 MHz, CDCl3) δ 190.0, 162.0, 154.6, 147.4, 140.9, 137.5, 132.8, 129.6, 127.9, 126.5, 125.8, 109.9, 17.6, 16.3.IR (KBr, ν / cm-1): 2925, 2863, 1682, 1604, 1586, 1480, 1465, 1377, 1269, 1239, 1186, 1125, 1084, 1026, 922, 884, 827, 786, 739, 718.HRMS (ESI): calcd. for C14H14NO2 ([M+H]+ ): 228.1019, found: 228.1023.
![Page 11: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/11.jpg)
11
O
O
N
MeMe
3-Methyl-2-((4-methylpyridin-2-yl)oxy)benzaldehyde (1u)White solid, M.p. 67 – 68 ℃, 1.56 g, 86%.1H NMR (300 MHz, CDCl3) δ 10.15 (d, J = 0.4 Hz, 1H), 7.94 (dd, J = 5.0, 2.5 Hz, 1H), 7.80 (d, J = 7.7 Hz, 1H), 7.52 (d, J = 6.9 Hz, 1H), 7.30 – 7.24 (m, 1H), 6.81 (d, J = 9.1 Hz, 2H), 2.37 (s, 3H), 2.16 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.8, 163.9, 154.4, 151.6, 147.2, 137.4, 132.7, 129.5, 126.4, 125.7, 120.1, 110.6, 21.2, 16.2.IR (KBr, ν / cm-1): 2956, 2858, 1698, 1682, 1611, 1588, 1564, 1467, 1390, 1289, 1250, 1188, 1149, 1085, 946, 923, 866, 819, 793, 781, 767, 734.HRMS (ESI): calcd. for C14H14NO2 ([M+H]+ ): 228.1019, found: 228.1028.
O
O
N
OMe
OMe
3-Methoxy-2-((5-methoxypyridin-2-yl)oxy)benzaldehyde (1v)White solid, M.p. 64 – 65 ℃, 1.43 g, 69%.1H NMR (300 MHz, CDCl3) δ 10.25 (d, J = 0.7 Hz, 1H), 7.72 (d, J = 3.1 Hz, 1H), 7.54 (ddd, J = 7.7, 1.6, 0.8 Hz, 1H), 7.35 – 7.18 (m, 3H), 7.00 (dd, J = 8.9, 0.5 Hz, 1H), 3.80 (s, 3H), 3.76 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.8, 158.0, 152.6, 152.4, 146.0, 132.1, 130.5, 126.8, 126.0, 119.5, 118.3, 110.9, 56.4, 56.2.IR (KBr, ν / cm-1): 2941, 2839, 1696, 1584, 1479, 1385, 1316, 1272, 1234, 1181, 1065, 1032, 1011, 886, 834, 774, 736, 715.HRMS (ESI): calcd. for C14H14NO4 ([M+H]+ ): 260.0917, found: 260.0928.
O
O
NF Me
5-Fluoro-2-((5-methylpyridin-2-yl)oxy)benzaldehyde (1w)Light yellow solid, M.p. 46 – 47 ℃, 1.24 g, 67%.1H NMR (300 MHz, CDCl3) δ 10.23 (d, J = 3.1 Hz, 1H), 7.95 (s, 1H), 7.67 – 7.53 (m, 2H), 7.38 – 7.26 (m, 1H), 7.15 (dd, J = 9.0, 4.3 Hz, 1H), 6.97 (d, J = 8.3 Hz, 1H), 2.29 (s, 3H).13C NMR (75 MHz, CDCl3) δ 188.3, 161.7, 159.5 (d, J = 246.3 Hz), 152.9 (d, J = 2.6
![Page 12: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/12.jpg)
12
Hz), 147.3, 141.0, 129.7 (d, J = 6.3 Hz), 129.0, 124.4 (d, J = 7.6 Hz), 122.6 (d, J = 24.1 Hz), 114.1 (d, J = 23.7 Hz), 111.2, 17.6.19F NMR (376 MHz, CDCl3) δ -116.6 (s).IR (KBr, ν / cm-1): 3023, 2866, 1690, 1604, 1581, 1472, 1425, 1377, 1244, 1183, 1141, 1027, 964, 881, 824, 744, 698.HRMS (ESI): calcd. for C13H11FNO2 ([M+H]+ ): 232.0768, found: 232.0778.
O
O
N
2-(Isoquinolin-1-yloxy)benzaldehyde (1x)White solid. 15%, 0.3 g.1H NMR (300 MHz, CDCl3) δ 10.29 (s, 1H), 8.47 (d, J = 8.1 Hz, 1H), 8.03 (dd, J = 7.8, 1.7 Hz, 1H), 7.94 (d, J = 5.9 Hz, 1H), 7.85 (d, J = 7.6 Hz, 1H), 7.81 – 7.74 (m, 1H), 7.73 – 7.65 (m, 2H), 7.43 – 7.30 (m, 3H).13C NMR (101 MHz, CDCl3) δ 189.2, 160.7, 156.5, 139.8, 138.8, 135.7, 131.4, 129.2, 128.9, 127.8, 126.7, 125.8, 124.1, 123.6, 119.6, 117.4; 1H and 13C NMR data agreed with literature [4].
O
O
N
2-(Quinolin-2-yloxy)benzaldehyde (1y)Light yellow soild. 57%, 1.1 g.1H NMR (300 MHz, CDCl3) δ 10.32 (d, J = 0.7 Hz, 1H), 8.17 (d, J = 8.8 Hz, 1H), 8.00 (dd, J = 7.8, 1.7 Hz, 1H), 7.74 (dd, J = 17.3, 8.1 Hz, 2H), 7.68 – 7.56 (m, 2H), 7.43 (t, J = 7.5 Hz, 1H), 7.34 (td, J = 8.5, 4.6 Hz, 2H), 7.20 (d, J = 8.8 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 189.3, 161.6, 156.3, 146.3, 140.5, 135.5, 130.2, 128.8, 128.7, 128.0, 127.6, 126.0, 125.4, 125.4, 123.1, 112.6; 1H and 13C NMR data agreed with literature [4].
O
O
CN
4-(2-Formylphenoxy)benzonitrile (1z)White solid, 0.89 g, 50%.1H NMR (300 MHz, CDCl3) δ 10.35 (d, J = 0.7 Hz, 1H), 7.99 (dd, J = 7.8, 1.8 Hz, 1H),
![Page 13: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/13.jpg)
13
7.69 – 7.64 (m, 3H), 7.39 – 7.33 (m, 1H), 7.13 – 7.06 (m, 2H), 7.05 (dd, J = 8.3, 0.7 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 188.6, 161.0, 157.4, 136.3, 134.6, 129.5, 128.0, 125.6, 120.7, 119.9, 118.6, 107.3; 1H and 13C NMR data agreed with literature [4].
O
O
CO2Me
Methyl 4-(2-formylphenoxy)benzoate (1aa)White solid, 0.80 g, 39%.1H NMR (300 MHz, CDCl3) δ 10.41 (d, J = 0.7 Hz, 1H), 8.09 – 8.03 (m, 2H), 7.97 (dd, J = 7.8, 1.8 Hz, 1H), 7.65 – 7.55 (m, 1H), 7.29 (dd, J = 8.3, 6.8 Hz, 1H), 7.12 – 6.98 (m, 3H), 3.91 (s, 3H).13C NMR (75 MHz, CDCl3) δ 188.9, 166.4, 161.0, 158.4, 136.1, 132.1, 128.9, 127.6, 125.7, 124.8, 120.1, 118.1, 52.3; 1H and 13C NMR data agreed with literature [4].
O
O
CF3
2-(4-(trifluoromethyl)phenoxy)benzaldehyde (1ab)Colorless oil, 0.92 g, 43%.1H NMR (400 MHz, CDCl3) δ 10.42 (s, 1H), 7.98 (dd, J = 7.8, 1.4 Hz, 1H), 7.69 – 7.51 (m, 3H), 7.30 (t, J = 7.5 Hz, 1H), 7.13 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.3 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 188.9, 159.9, 158.5, 136.2, 129.2, 127.8, 127.7 (q, J = 3.7 Hz), 126.3 (d, J = 33.0 Hz), 124.9, 124.2 (d, J = 271.7 Hz), 119.9, 118.7; 1H and 13C NMR data agreed with literature [5].
O
OF
2-(2-Fluorophenoxy)benzaldehyde (1ac)White solid, 0.94 g, 54%.1H NMR (300 MHz, CDCl3) δ 10.62 (d, J = 0.7 Hz, 1H), 7.94 (dd, J = 7.7, 1.8 Hz, 1H), 7.49 (ddd, J = 8.4, 7.3, 1.8 Hz, 1H), 7.25 – 7.11 (m, 5H), 6.79 (d, J = 8.4 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 189.2, 160.1, 154.5 (d, J = 249.6 Hz), 142.7 (d, J = 11.2 Hz), 135.9, 128.6, 126.2 (d, J = 6.9 Hz), 125.9, 125.2 (d, J = 4.0 Hz), 123.3, 122.8, 117.5 (d, J = 18.0 Hz), 116.3; 1H and 13C NMR data agreed with literature [6].
![Page 14: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/14.jpg)
14
O
OBr
Cl
2-(2-bromo-4-chlorophenoxy)benzaldehyde (1ad)
Colorless oil, 1.62 g, 65%.
1H NMR (400 MHz, CDCl3) δ 10.56 (s, 1H), 7.96 (dd, J = 7.7, 1.7 Hz, 1H), 7.66 (d, J = 2.3 Hz, 1H), 7.54 – 7.47 (m, 1H), 7.41 (dd, J = 8.7, 2.3 Hz, 1H), 7.22 (t, J = 7.5 Hz, 1H), 6.96 (d, J = 8.7 Hz, 1H), 6.74 (d, J = 8.3 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 189.0, 159.2, 150.9, 136.0, 133.9, 131.6, 129.1, 127.8, 126.4, 124.0, 123.0, 118.0, 117.0.IR (KBr, ν / cm-1): 3125, 2919, 2873, 1690, 1652, 1601, 1541, 1469, 1456, 1396, 1258, 1236, 1197, 1132, 1079, 1057, 823, 760, 742.HRMS (ESI): calcd. for C13H9BrClO2 ([M+H]+ ): 312.9448, found: 312.9455.
O
OMe
Me
2-(2,6-Dimethylphenoxy)benzaldehyde (1ae)Light yellow solid, M.p. 62 – 63 ℃, 0.87 g, 48%.1H NMR (300 MHz, CDCl3) δ 10.78 (d, J = 0.7 Hz, 1H), 7.93 (dd, J = 7.7, 1.8 Hz, 1H), 7.49 – 7.33 (m, 1H), 7.19 – 7.11 (m, 3H), 7.07 (dd, J = 11.7, 4.2 Hz, 1H), 6.44 (d, J = 8.4 Hz, 1H), 2.15 (s, 6H).13C NMR (75 MHz, CDCl3) δ 189.5, 160.3, 150.4, 136.1, 131.3, 129.4, 128.7, 125.9, 124.4, 121.7, 115.3, 113.6, 16.5.IR (KBr, ν / cm-1): 2981, 2854, 1690, 1651, 1600, 1581, 1474, 1456, 1395, 1267, 1224, 1180, 1156, 1099, 1089, 1035, 876, 825, 800, 762.HRMS (ESI): calcd. for C15H15O2 ([M+H]+ ): 227.1607, found: 227.1068.
O
OOMe
2-(2-Methoxyphenoxy)benzaldehyde (1af)White solid, 0.84 g, 46%.1H NMR (300 MHz, CDCl3) δ 10.65 (d, J = 0.8 Hz, 1H), 7.91 (dd, J = 7.7, 1.8 Hz, 1H), 7.43 (ddd, J = 8.4, 7.3, 1.8 Hz, 1H), 7.21 (ddd, J = 8.1, 7.4, 1.8 Hz, 1H), 7.14 – 6.93
![Page 15: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/15.jpg)
15
(m, 4H), 6.75 – 6.67 (m, 1H), 3.78 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.7, 161.0, 151.6, 143.8, 135.7, 128.1, 126.2, 125.6, 122.5, 122.1, 121.3, 116.3, 113.0, 55.9; 1H and 13C NMR data agreed with literature [2].
O
OOMe
OMe
2-(2,6-Dimethoxyphenoxy)benzaldehyde (1ag)White solid, M.p. 110 – 111 ℃, 1.09 g, 53%.1H NMR (300 MHz, CDCl3) δ 10.77 (d, J = 0.7 Hz, 1H), 7.89 (dd, J = 7.7, 1.8 Hz, 1H), 7.38 (ddd, J = 8.5, 7.3, 1.8 Hz, 1H), 7.18 (t, J = 8.4 Hz, 1H), 7.05 (t, J = 7.5 Hz, 1H), 6.72 – 6.55 (m, 3H), 3.77 (s, 6H).13C NMR (75 MHz, CDCl3) δ 190.1, 161.5, 153.5, 135.6, 132.0, 127.9, 126.2, 125.1, 121.9, 114.9, 109.9, 105.4, 56.3.IR (KBr, ν / cm-1): 2996, 2832, 1684, 1599, 1480, 1444, 1397, 1303, 1280, 1257, 1235, 1184, 1157, 1033, 875, 823, 799, 768, 750, 735, 701. HRMS (ESI): calcd. for C15H15O4 ([M+H]+ ): 259.0965, found: 259.0964.
IV. UV-vis absorption spectra of 1a
250 275 300 325 350 375 4000.00
0.25
0.50
0.75
1.00
Abs
orba
nce
(a. u
.)
Wavelength (nm)
C1a = 5.0 x 10-5 M
Figure S1 UV-vis absorption spectra of 1a
![Page 16: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/16.jpg)
16
V. General procedures for heteroaryl/aryl rearrangement
i. General procedures for heteroaryl rearrangement
The starting materials 1 (0.2 mmol), TFA (0.2 mmol) were added into 2.0 mL of ethyl acetate in an airtight quartz tube, which was then evacuated by four freeze-pump-thaw cycles and back-filled with ultra-purified argon prior to use. The reaction was stirred at room temperature under UV irradiation (254 nm) for 24 h and 5 mL saturated NaHCO3 aqueous solution was added into the reaction solution, and extracted with 3 × 5 mL EtOAc. The combined organic phases were washed with brine, dried over anhydrous MgSO4 and concentrated under reduced pressure. Purification by column chromatography on silica (PE/EA = 20/1) affords 2.
ii. General procedures for aryl rearrangement
The starting materials 1 (0.2 mmol) were added into 2.0 mL of ethyl acetate in an airtight quartz tube, which was then evacuated by four freeze-pump-thaw cycles and back-filled with ultra-purified argon prior to use. The reaction was stirred at room temperature under UV irradiation (254 nm) for 24 h. The reaction mixture was concentrated under reduced pressure. Purification by column chromatography on silica (PE/EA = 30/1) affords 2.
VI. Characterization data of rearrangement products
OH
ON
(2-Hydroxyphenyl)(pyridin-2-yl)methanone (2a) Yellow oil. 33.1 mg, 83%.1H NMR (300 MHz, CDCl3) δ 12.36 (s, 1H), 8.73 (dt, J = 4.8, 1.4 Hz, 1H), 8.11 (dd, J = 8.1, 1.7 Hz, 1H), 7.96 – 7.89 (m, 2H), 7.56 – 7.47 (m, 2H), 7.06 (dd, J = 8.4, 0.7 Hz, 1H), 6.90 (ddd, J = 8.2, 7.2, 1.2 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ 197.4, 163.6, 155.4, 148.4, 137.6, 136.8, 134.5, 126.3, 124.8, 119.3, 119.0, 118.6; 1H and 13C NMR data agreed with literature[4].
OH
O
N
Me
(2-Hydroxyphenyl)(3-methylpyridin-2-yl)methanone (2b)
![Page 17: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/17.jpg)
17
Light yellow oil. 34.5 mg, 81%.1H NMR (300 MHz, CDCl3) δ 12.08 (s, 1H), 8.52 (dd, J = 4.7, 0.7 Hz, 1H), 7.67 (d, J = 7.8 Hz, 1H), 7.53 – 7.48 (m, 1H), 7.40 – 7.32 (m, 2H), 7.06 (dd, J = 8.4, 1.0 Hz, 1H), 6.88 – 6.76 (m, 1H), 2.37 (s, 3H).13C NMR (75 MHz, CDCl3) δ 200.6, 163.9, 154.4, 146.2, 139.2, 137.2, 133.7, 132.0, 124.8, 119.2, 119.1, 118.4, 18.2. IR (KBr, ν / cm-1): 3052, 2933, 1694, 1638, 1485, 1455, 1340, 1149, 1107, 1062, 1034, 944, 864, 795, 762.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0860.
OH
ON
Me
(2-Hydroxyphenyl)(4-methylpyridin-2-yl)methanone (2c)Yellow oil. 30.2 mg, 71%.1H NMR (300 MHz, CDCl3) δ 12.53 (s, 1H), 8.57 (d, J = 5.0 Hz, 1H), 8.09 (dd, J = 8.1, 1.7 Hz, 1H), 7.77 – 7.76 (m, 1H), 7.54 – 7.46 (m, 1H), 7.33 (ddd, J = 5.0, 1.6, 0.7 Hz, 1H), 7.05 (dd, J = 8.4, 1.1 Hz, 1H), 6.90 (ddd, J = 8.2, 7.2, 1.2 Hz, 1H), 2.47 (s, 3H).13C NMR (75 MHz, CDCl3) δ 197.5, 163.3, 155.2, 149.2, 148.0, 136.7, 134.4, 127.2, 125.5, 119.7, 119.0, 118.6, 21.4. IR (KBr, ν / cm-1): 3058, 2920, 1627, 1599, 1485, 1444, 1330, 1308, 1258, 1211, 1161, 954, 855, 807, 756, 661.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0861.
OH
ON
Me
(2-Hydroxyphenyl)(5-methylpyridin-2-yl)methanone (2d)Light yellow solid, M.p. 77 – 78 ℃. 38.3 mg, 90%.1H NMR (300 MHz, CDCl3) δ 12.51 (s, 1H), 8.54 (dd, J = 1.4, 0.6 Hz, 1H), 8.17 (dd, J = 8.1, 1.7 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 7.71 (ddd, J = 8.0, 2.1, 0.5 Hz, 1H), 7.49 (ddd, J = 8.8, 7.2, 1.7 Hz, 1H), 7.06 – 7.02 (m, 1H), 6.93 – 6.86 (m, 1H), 2.45 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 196.9, 163.3, 152.8, 148.7, 138.0, 136.9, 136.5, 134.4, 124.6, 119.6, 118.9, 118.6, 18.8. IR (KBr, ν / cm-1): 3037, 2926, 1627, 1567, 1477, 1491, 1381, 1336, 1318, 1148, 1142,
![Page 18: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/18.jpg)
18
1084, 943, 849, 799, 786, 691.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0860.
OH
ON
OMe
(2-Hydroxyphenyl)(5-methoxypyridin-2-yl)methanone (2e)Yellow oil. 44.0 mg, 96%.1H NMR (300 MHz, CDCl3) δ 12.46 (s, 1H), 8.38 (d, J = 2.7 Hz, 1H), 8.31 (d, J = 8.1 Hz, 1H), 8.02 (d, J = 8.7 Hz, 1H), 7.49 (t, J = 7.1 Hz, 1H), 7.35 (dd, J = 8.7, 2.8 Hz, 1H), 7.04 (d, J = 8.3 Hz, 1H), 6.91 (t, J = 7.6 Hz, 1H), 3.95 (s, 3H).13C NMR (75 MHz, CDCl3) δ 195.8, 163.3, 157.8, 147.8, 136.4 (d, J = 4.4 Hz), 134.5, 126.7, 120.6, 119.5, 118.8, 118.4, 56.0. IR (KBr, ν / cm-1): 3013, 2970, 2942, 2844, 1623, 1570, 1477, 1442, 1395, 1272, 1148, 1026, 941, 829, 805, 758, 687. HRMS (ESI): calcd. for C13H12NO3 ([M+H]+ ): 230.0812, found: 230.0811.
OH
ON OMe
(2-Hydroxyphenyl)(6-methoxypyridin-2-yl)methanone (2f)Yellow oil. 26.1 mg, 57%.1H NMR (300 MHz, CDCl3) δ 12.24 (s, 1H), 8.27 (dd, J = 8.1, 1.7 Hz, 1H), 7.77 (dd, J = 8.3, 7.3 Hz, 1H), 7.56 – 7.45 (m, 2H), 7.06 (dd, J = 8.4, 1.1 Hz, 1H), 6.96 (dd, J = 8.4, 0.7 Hz, 1H), 6.93 – 6.85 (m, 1H), 3.97 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 197.5, 164.0, 163.0, 152.8, 139.5, 136.7, 134.4, 119.0, 118.6, 118.4, 118.0, 114.4, 54.0. IR (KBr, ν / cm-1): 3080, 3015, 2983, 2952, 2857, 1630, 1586, 1468, 1436, 1345, 1293, 1246, 1151, 1079, 971, 875, 825, 792, 730, 687. HRMS (ESI): calcd. for C13H12NO3 ([M+H]+ ): 230.0812, found: 230.0809.
OH
ON
F
(5-Fluoropyridin-2-yl)(2-hydroxyphenyl)methanone (2g)Yellow solid, M.p. 72 – 73 ℃. 34.7 mg, 80%.1H NMR (300 MHz, CDCl3) δ 12.12 (s, 1H), 8.58 (d, J = 2.6 Hz, 1H), 8.20 – 8.14 (m,
![Page 19: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/19.jpg)
19
1H), 8.02 (dd, J = 8.7, 4.5 Hz, 1H), 7.62 (td, J = 8.3, 2.7 Hz, 1H), 7.52 (t, J = 7.1 Hz, 1H), 7.06 (d, J = 8.4 Hz, 1H), 6.92 (t, J = 7.4 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ 196.0, 164.0, 160.7 (d, J = 263.3 Hz), 151.7, 137.0 (d, J = 24.2 Hz), 137.0, 134.5, 126.8 (d, J = 5.4 Hz), 124.2 (d, J = 18.5 Hz), 119.0, 118.6, 118.5. 19F NMR (376 MHz, CDCl3) δ -120.5 (dd, J = 8.0, 4.6 Hz).IR (KBr, ν / cm-1): 2918, 2875, 2853, 1627, 1584, 1566, 1513, 1384, 1261, 1224, 1181, 1149, 1049, 1034, 941, 872, 792, 751, 690. HRMS (ESI): calcd. for C12H9FNO2 ([M+H]+ ): 218.0612, found: 218.0611.
OH
ON
Cl
(5-Chloropyridin-2-yl)(2-hydroxyphenyl)methanone (2h)Light yellow solid, M.p. 89 – 90 ℃. 33.6 mg, 72%.1H NMR (300 MHz, CDCl3) δ 12.09 (s, 1H), 8.69 (s, 1H), 8.15 (d, J = 8.1 Hz, 1H), 7.91 (s, 2H), 7.53 (t, J = 7.8 Hz, 1H), 7.06 (d, J = 8.4 Hz, 1H), 6.91 (t, J = 7.6 Hz, 1H).
13C NMR (75 MHz, CDCl3) δ 196.3, 163.9, 153.3, 147.5, 137.3, 137.1, 135.2, 134.3, 125.8, 119.0, 118.5. IR (KBr, ν / cm-1): 3054, 2998, 2924, 2867, 1627, 1572, 1483, 1461, 1373, 1310, 1248, 1112, 1015, 941, 851, 825, 801, 754, 734, 730, 691. HRMS (ESI): calcd. for C12H9ClNO2 ([M+H]+ ): 234.0316, found: 234.0321.
OH
ON
Br
(5-bromopyridin-2-yl)(2-hydroxyphenyl)methanone (2i)Light yellow solid, M.p. 103 – 104 ℃. 37.3 mg, 67%.1H NMR (300 MHz, CDCl3) δ 12.07 (s, 1H), 8.79 (dd, J = 2.2, 0.6 Hz, 1H), 8.14 (dd, J = 8.1, 1.6 Hz, 1H), 8.05 (dd, J = 8.4, 2.3 Hz, 1H), 7.83 (dd, J = 8.4, 0.6 Hz, 1H), 7.52 (ddd, J = 8.7, 7.3, 1.6 Hz, 1H), 7.05 (dd, J = 8.4, 1.0 Hz, 1H), 6.90 (ddd, J = 8.2, 7.2, 1.2 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 196.5, 163.9, 153.8, 149.7, 140.2, 137.1, 134.3, 126.1, 124.3, 119.1, 118.6, 118.5.IR (KBr, ν / cm-1): 3027, 2948, 2879, 1627, 1565, 1483, 1445, 1369, 1333, 1310, 1251,
![Page 20: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/20.jpg)
20
1230, 1148, 1112, 1088, 1008, 940, 849, 824, 800, 755, 667. HRMS (ESI): calcd. for C12H9BrNO2 ([M+H]+ ): 277.9811, found: 277.9814.
OH
ON
CF3
(2-Hydroxyphenyl)(5-(trifluoromethyl)pyridin-2-yl)methanone (2j)Yellow oil. 25.1 mg, 47%.1H NMR (300 MHz, CDCl3) δ 11.97 (s, 1H), 9.01 (dd, J = 1.4, 0.7 Hz, 1H), 8.23 – 8.12 (m, 1H), 8.03 (ddd, J = 8.2, 3.6, 1.1 Hz, 2H), 7.55 (ddd, J = 8.5, 7.2, 1.7 Hz, 1H), 7.13 – 7.03 (m, 1H), 6.98 – 6.86 (m, 1H). 13C NMR (75 MHz, CDCl3) δ 196.5, 164.2, 158.5, 145.6 (q, J = 4.0 Hz), 137.5, 134.8 (q, J = 3.5 Hz), 134.3, 128.6 (d, J = 33.5 Hz), 124.4, 123.2 (d, J = 272.9 Hz), 119.2, 118.7, 118.4.19F NMR (376 MHz, CDCl3) δ -62.6 (s).IR (KBr, ν / cm-1): 3080, 2922, 1630, 1571, 1487, 1448, 1394, 1325, 1258, 1243, 1170, 1148, 1017, 943, 815, 786. HRMS (ESI): calcd. for C13H9F3NO2 ([M+H]+ ): 268.0580, found: 268.0583.
O
S
N
OH
Benzo[d]thiazol-2-yl(2-hydroxyphenyl)methanone (2k)Yellow solid, M.p. 89 – 90 ℃. 29.2 mg, 57%.1H NMR (300 MHz, CDCl3) δ 12.10 (s, 1H), 9.25 (dd, J = 8.2, 1.7 Hz, 1H), 8.29 – 8.18 (m, 1H), 8.04 – 7.95 (m, 1H), 7.65 – 7.50 (m, 3H), 7.10 – 6.98 (m, 2H). 13C NMR (75 MHz, CDCl3) δ 187.8, 167.2, 164.3, 153.8, 137.7, 136.9, 134.2, 128.0, 127.3, 125.9, 122.3, 119.7, 118.6, 118.3; 1H and 13C NMR data agreed with literature [4].
OH
O
N
N Me
Me
(3,6-Dimethylpyrazin-2-yl)(2-hydroxyphenyl)methanone (2l)Light yellow oil. 36.9 mg, 81%.1H NMR (300 MHz, CDCl3) δ 11.93 (s, 1H), 8.52 (s, 1H), 7.54 (ddd, J = 8.6, 7.2, 1.7 Hz, 1H), 7.30 (dd, J = 8.0, 1.7 Hz, 1H), 7.08 (dd, J = 8.5, 1.0 Hz, 1H), 6.85 (ddd, J =
![Page 21: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/21.jpg)
21
8.2, 7.2, 1.1 Hz, 1H), 2.60 (s, 3H), 2.55 (s, 3H).13C NMR (75 MHz, CDCl3) δ 199.4, 164.1, 150.1, 148.8, 148.6, 144.9, 137.7, 133.5, 119.3, 118.9, 118.7, 21.2, 21.1.IR (KBr, ν / cm-1): 3047, 3067, 2929, 2858, 1630, 1576, 1485, 1448, 1371, 1254, 1215, 1138, 1108, 1034, 1004, 952, 885, 864, 820, 756, 736, 691. HRMS (ESI): calcd. for C13H13N2O2 ([M+H]+ ): 229.0972, found: 229.0971.
OH
ON
Me
(2-Hydroxy-4-methylphenyl)(pyridin-2-yl)methanone (2m)Light yellow solid, M.p. 32 – 33 ℃. 32.4 mg, 76%.1H NMR (300 MHz, CDCl3) δ 12.38 (s, 1H), 8.72 (d, J = 4.7 Hz, 1H), 7.99 (d, J = 8.3 Hz, 1H), 7.91 (d, J = 3.7 Hz, 2H), 7.49 (dd, J = 8.9, 4.7 Hz, 1H), 6.86 (s, 1H), 6.72 (d, J = 8.3 Hz, 1H), 2.37 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 196.9, 163.9, 155.6, 148.7, 148.4, 137.5, 134.3, 126.1, 124.6, 120.4, 118.6, 116.8, 22.2. IR (KBr, ν / cm-1): 3060, 2985, 2924, 1641, 1584, 1556, 1504, 1345, 1308, 1261, 1171, 1047, 997, 870, 793, 785, 703. HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0869.
OH
ON
Me
(2-Hydroxy-3-methylphenyl)(pyridin-2-yl)methanone (2n)Yellow solid, M.p. 42 – 45 ℃. 36.2 mg, 85%.1H NMR (300 MHz, CDCl3) δ 12.53 (s, 1H), 8.72 (dd, J = 4.9, 1.0 Hz, 1H), 7.94 – 7.88 (m, 3H), 7.51 – 7.46 (m, 1H), 7.38 (d, J = 7.2 Hz, 1H), 6.80 (t, J = 7.7 Hz, 1H), 2.31 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 198.1, 162.2, 155.7, 148.5, 137.6, 137.4, 132.0, 127.4, 126.0, 124.6, 118.3, 118.2, 15.9. IR (KBr, ν / cm-1): 3056, 3015, 2955, 2922, 1623, 1584, 1479, 1423, 1340, 1304, 1258, 1194, 1032, 995, 853, 780, 751, 687. HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0871.
![Page 22: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/22.jpg)
22
OH
ON
OMe
(2-Hydroxy-3-methoxyphenyl)(pyridin-2-yl)methanone (2o)Yellow solid, M.p. 85 – 86 ℃. 23.4 mg, 51%. 1H NMR (300 MHz, CDCl3) δ 12.78 (s, 1H), 8.73 (d, J = 4.8 Hz, 1H), 8.01 – 7.87 (m, 2H), 7.69 (dd, J = 8.3, 1.2 Hz, 1H), 7.58 – 7.49 (m, 1H), 7.11 (d, J = 8.0 Hz, 1H), 6.86 (t, J = 8.1 Hz, 1H), 3.94 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 197.3, 155.3, 153.7, 149.2, 148.2, 137.7, 126.4, 125.5, 124.8, 119.9, 118.4, 117.3, 56.4. IR (KBr, ν / cm-1): 3054, 3009, 2924, 2851, 1630, 1586, 1453, 1436, 1340, 1310, 1254, 1194, 1079, 985, 842, 803, 784, 747, 698.HRMS (ESI): calcd. for C13H12NO3 ([M+H]+ ): 230.0812, found: 230.0816.
OH
ONBr
(5-bromo-2-hydroxyphenyl)(pyridin-2-yl)methanone (2p)Yellow solid, M.p. 69 – 70 ℃. 43.4 mg, 78%.1H NMR (300 MHz, CDCl3) δ 12.63 (s, 1H), 8.75 – 8.73(m, 1H), 8.37 (d, J = 2.5 Hz, 1H), 8.04 – 7.92 (m, 2H), 7.59 – 7.54 (m, 2H), 6.96 (d, J = 8.9 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 195.3, 162.1, 154.6, 148.2, 139.3, 138.0, 136.4, 126.9, 125.1, 121.1, 120.8, 110.7.IR (KBr, ν / cm-1): 3081, 2996, 1627, 1604, 1584, 1566, 1460, 1433, 1383, 1332, 1283, 1332, 1283, 1236, 1152, 1094, 1047, 1022, 995, 947, 901, 828, 750, 676. HRMS (ESI): calcd. for C12H9BrNO2 ([M+H]+ ): 277.9811, found: 277.9815.
OH
ONF
(5-Fluoro-2-hydroxyphenyl)(pyridin-2-yl)methanone (2q)Yellow solid, M.p. 48 – 49 ℃. 35.6 mg, 82%.1H NMR (300 MHz, CDCl3) δ 12.33 (s, 1H), 8.74 (d, J = 4.7 Hz, 1H), 8.05 – 7.99 (m, 2H), 7.95 (td, J = 7.7, 1.7 Hz, 1H), 7.55 (ddd, J = 7.3, 4.8, 1.4 Hz, 1H), 7.30 – 7.21 (m, 1H), 7.02 (dd, J = 9.1, 4.6 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ 195.5, 159.6, 154.9 (d, J = 237.3 Hz), 154.8, 148.2,
![Page 23: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/23.jpg)
23
137.9, 126.8, 125.0, 124.4 (d, J = 24.0 Hz), 119.9 (d, J = 7.4 Hz), 119.2 (d, J = 24.5 Hz), 119.2.19F NMR (376 MHz, CDCl3) δ -124.3 (ddd, J = 9.8, 7.6, 4.6 Hz).IR (KBr, ν / cm-1): 3093, 3060, 2920, 1641, 1615, 1584, 1485, 1422, 1343, 1284, 1252, 1138, 995, 980, 874, 833, 790, 672. HRMS (ESI): calcd. for C12H9FNO2 ([M+H]+ ): 218.0612, found: 218.0611.
OH
ONCl
(5-Chloro-2-hydroxyphenyl)(pyridin-2-yl)methanone (2r)Yellow solid, M.p. 42 – 43 ℃. 36.8 mg, 79%.1H NMR (300 MHz, CDCl3) δ 12.60 (s, 1H), 8.75 (d, J = 4.8 Hz, 1H), 8.24 (d, J = 2.7 Hz, 1H), 8.07 – 7.90 (m, 2H), 7.63 – 7.53 (m, 1H), 7.44 (dd, J = 8.9, 2.6 Hz, 1H), 7.01 (d, J = 8.9 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ 195.4, 161.7, 154.6, 148.2, 138.0, 136.5, 133.4, 126.9, 125.1, 123.7, 120.3, 120.2. IR (KBr, ν / cm-1): 3019, 2968, 2920, 2799, 1632, 1587, 1567, 1463, 1435, 1390, 1336, 1287, 1237, 1157, 1130, 1025, 997, 874, 833, 752, 730, 692. HRMS (ESI): calcd. for C12H9ClNO2 ([M+H]+ ): 234.0316, found: 234.0316.
OH
ON
OMeMe
(2-Hydroxy-3-methylphenyl)(5-methoxypyridin-2-yl)methanone (2s)Yellow solid, M.p. 65 – 66 ℃. 46.2 mg, 95%.1H NMR (300 MHz, CDCl3) δ 12.63 (s, 1H), 8.38 (d, J = 2.9 Hz, 1H), 8.09 (dd, J = 8.2, 1.7 Hz, 1H), 7.97 (d, J = 8.7 Hz, 1H), 7.34 (dt, J = 8.8, 4.3 Hz, 2H), 6.86 – 6.73 (m, 1H), 3.93 (s, 3H), 2.30 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 196.5, 162.0, 157.6, 148.1, 137.2, 136.5, 132.1, 127.2, 126.5, 120.4, 118.5, 118.1, 55.9, 15.9. IR (KBr, ν / cm-1): 3054, 2976, 2929, 2845, 1619, 1578, 1476, 1423, 1341, 1306, 1267, 1241, 1135, 1039, 1023, 978, 874, 853, 814, 740, 704. HRMS (ESI): calcd. for C14H14NO3 ([M+H]+ ): 244.0968, found: 244.0971.
![Page 24: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/24.jpg)
24
OH
ON
MeMe
(2-Hydroxy-3-methylphenyl)(5-methylpyridin-2-yl)methanone (2t)Yellow solid, M.p. 43 – 44 ℃. 40.4 mg, 89%.1H NMR (300 MHz, CDCl3) δ 12.63 (s, 1H), 8.54 (dd, J = 1.4, 0.7 Hz, 1H), 7.95 (ddd, J = 8.2, 1.7, 0.5 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.73 – 7.65 (m, 1H), 7.37 (d, J = 7.2 Hz, 1H), 6.85 – 6.72 (m, 1H), 2.44 (s, 3H), 2.31 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 197.8, 162.0, 153.0, 148.9, 137.7, 137.4, 136.5, 132.0, 127.3, 124.4, 118.5, 118.2, 18.8, 15.9. IR (KBr, ν / cm-1): 3025, 3012, 2931, 1633, 1575, 1497, 1412, 1367, 1304, 1222, 1180, 1032, 995, 853, 789, 751, 686. HRMS (ESI): calcd. for C14H14NO2 ([M+H]+ ): 228.1019, found: 228.1027.
OH
ON
MeMe
(2-Hydroxy-3-methylphenyl)(4-methylpyridin-2-yl)methanone (2u)Yellow oil. 30.9 mg, 68%.1H NMR (300 MHz, CDCl3) δ 12.62 (s, 1H), 8.57 (d, J = 5.0 Hz, 1H), 7.88 (ddd, J = 8.1, 1.1, 0.5 Hz, 1H), 7.76 – 7.66 (m, 1H), 7.39 – 7.35 (m, 1H), 7.30 (ddd, J = 5.0, 1.6, 0.7 Hz, 1H), 6.80 (t, J = 7.7 Hz, 1H), 2.46 (s, 3H), 2.31 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 198.3, 162.0, 155.5, 148.9, 148.2, 137.5, 132.0, 127.4, 126.9, 125.3, 118.5, 118.3, 21.3, 15.9. IR (KBr, ν / cm-1): 3054, 2955, 2924, 1620, 1599, 1559, 1477, 1451, 1425, 1330, 1256, 1170, 1086, 1051, 997, 812, 799, 783, 751, 697.HRMS (ESI): calcd. for C14H14NO2 ([M+H]+ ): 228.1019, found: 228.1023.
OH
ON
OMeOMe
(2-Hydroxy-3-methoxyphenyl)(5-methoxypyridin-2-yl)methanone (2v)Yellow solid, M.p. 88 – 89 ℃. 28.0 mg, 54%.1H NMR (300 MHz, CDCl3) δ 12.83 (s, 1H), 8.37 (d, J = 2.9 Hz, 1H), 8.05 (d, J = 8.8 Hz, 1H), 7.87 (dd, J = 8.3, 1.3 Hz, 1H), 7.37 (dd, J = 8.8, 2.9 Hz, 1H), 7.09 (d, J = 7.9 Hz, 1H), 6.86 (t, J = 8.1 Hz, 1H), 3.96 (s, 3H), 3.93 (s, 3H).
![Page 25: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/25.jpg)
25
13C NMR (75 MHz, CDCl3) δ 195.8, 157.9, 153.5, 149.1, 147.8, 136.2, 126.7, 125.6, 120.8, 120.1, 118.1, 116.9, 56.4, 56.0. IR (KBr, ν / cm-1): 3058, 3006, 2940, 2840, 1625, 1576, 1451, 1436, 1343, 1313, 1250, 1189, 1178, 985, 844, 779, 738, 687. HRMS (ESI): calcd. for C14H14NO4 ([M+H]+ ): 260.0917, found: 260.0917.
OH
ONF
Me
(5-Fluoro-2-hydroxyphenyl)(5-methylpyridin-2-yl)methanone (2w)Yellow solid, M.p. 81 – 82 ℃. 43.0 mg, 93%. 1H NMR (300 MHz, CDCl3) δ 12.52 (s, 1H), 8.57 – 8.52 (m, 1H), 8.07 (dd, J = 9.9, 3.2 Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.81 – 7.68 (m, 1H), 7.33 – 7.17 (m, 1H), 7.00 (dd, J = 9.1, 4.7 Hz, 1H), 2.47 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 195.1, 159.4, 154.9 (d, J = 236.8 Hz), 152.2, 148.5, 138.3, 137.5, 124.9, 124.1 (d, J = 23.9 Hz), 119.9 (d, J = 7.4 Hz), 119.6 (d, J = 6.8 Hz), 119.2 (d, J = 24.7 Hz), 18.9.19F NMR (376 MHz, CDCl3) δ -124.5 (ddd, J = 9.8, 7.5, 4.7 Hz).IR (KBr, ν / cm-1): 3037, 2965, 2931, 1638, 1612, 1593, 1479, 1422, 1384, 1343, 1287, 1218, 1136, 1034, 976, 874, 833, 784, 728, 687. HRMS (ESI): calcd. for C13H11FNO2 ([M+H]+ ): 232.0768, found: 230.0777.
OH
O
CN
4-(2-Hydroxybenzoyl)benzonitrile (2z)Yellow solid, M.p. 121 – 122 ℃. 17.0 mg, 38%.1H NMR (300 MHz, CDCl3) δ 11.79 (s, 1H), 7.85 – 7.80 (m, 2H), 7.79 – 7.74 (m, 2H), 7.56 (ddd, J = 8.6, 7.3, 1.7 Hz, 1H), 7.45 (dd, J = 8.1, 1.6 Hz, 1H), 7.10 (dd, J = 8.4, 0.9 Hz, 1H), 6.90 (ddd, J = 8.2, 7.2, 1.1 Hz, 1H).13C NMR (151 MHz, CDCl3) δ 199.7, 163.4, 141.6, 137.2, 133.0, 132.2, 129.4, 119.0, 118.8, 118.5, 117.9, 115.3; 1H and 13C NMR data agreed with literature [4].
OH
O
CO2Me
Methyl 4-(2-hydroxybenzoyl)benzoate (2aa)
![Page 26: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/26.jpg)
26
White solid, M.p. 97 – 98 ℃. 22.0 mg, 43%.1H NMR (300 MHz, CDCl3) δ 11.93 (s, 1H), 8.21 – 8.12 (m, 2H), 7.75 – 7.68 (m, 2H), 7.57 – 7.47 (m, 2H), 7.09 (ddd, J = 8.3, 1.1, 0.6 Hz, 1H), 6.89 (ddd, J = 8.2, 7.2, 1.1 Hz, 1H), 3.98 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 201.1, 167.0, 166.4, 163.5, 141.8, 137.0, 133.5, 133.0, 129.7, 129.1, 119.1, 118.8, 52.7; 1H and 13C NMR data agreed with literature [4].
OH
O
CF3
(2-Hydroxyphenyl)(4-(trifluoromethyl)phenyl)methanone (2ab)White solid, M.p. 49 – 50 ℃. 17.6 mg, 33%.1H NMR (300 MHz, CDCl3) δ 11.89 (s, 1H), 7.79 (s, 4H), 7.65 – 7.46 (m, 2H), 7.10 (dd, J = 8.4, 1.1 Hz, 1H), 6.90 (ddd, J = 8.2, 7.2, 1.1 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 200.6, 163.6, 141.2, 137.2, 133.6 (d, J = 32.7 Hz), 133.5, 129.5, 125.6 (q, J = 3.7 Hz), 123.8 (d, J = 272.6 Hz), 119.2, 118.9, 118.9; 1H and 13C NMR data agreed with literature [8].
OH
O F
(2-Fluorophenyl)(2-hydroxyphenyl)methanone (2ac)Light yellow oil. 21.6 mg, 50%.1H NMR (300 MHz, CDCl3) δ 11.98 (s, 1H), 7.60 – 7.38 (m, 4H), 7.30 (td, J = 7.5, 1.0 Hz, 1H), 7.21 (ddd, J = 9.5, 8.4, 0.9 Hz, 1H), 7.07 (dd, J = 8.4, 1.1 Hz, 1H), 6.87 (ddd, J = 8.2, 7.2, 1.1 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 198.7, 163.2, 159.3 (d, J = 251.5 Hz), 137.3, 133.6 (d, J = 2.2 Hz), 133.1 (d, J = 8.2 Hz), 130.1 (d, J = 2.9 Hz), 126.5 (d, J = 15.9 Hz), 124.6 (d, J = 3.6 Hz), 119.9, 119.2, 118.5, 116.5 (d, J = 21.3 Hz).19F NMR (376 MHz, CDCl3) δ -112.2 – -112.3 (m).IR (KBr, ν / cm-1): 3063, 2920, 2862, 1630, 1615, 1580, 1485, 1451, 1336, 1269, 1246, 1220, 1146, 937, 834, 816, 754, 685. HRMS (ESI): calcd. for C13H10FO2 ([M+H]+ ): 217.0659, found: 217.0663.
O
OH
Br
Cl
![Page 27: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/27.jpg)
27
(2-Bromo-4-chlorophenyl)(2-hydroxyphenyl)methanone (2ad)
Light yellow oil. 27.4 mg, 44%.1H NMR (400 MHz, CDCl3) δ 11.83 (s, 1H), 7.68 (d, J = 1.8 Hz, 1H), 7.57 – 7.48 (m, 2H), 7.25 – 7.20 (m, 2H), 7.07 (dd, J = 8.4, 0.8 Hz, 1H), 6.84 (ddd, J = 8.1, 7.3, 1.1 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 199.7, 163.4, 137.6, 136.4, 133.4, 133.0, 132.2, 130.3, 129.9, 124.9, 119.4, 119.3, 118.7.IR (KBr, ν / cm-1): 3085, 2971, 2851, 1628, 1579, 1485, 1454, 1371, 1337, 1308, 1243, 1219, 1148, 1114, 1084, 935, 833, 777, 757, 656.HRMS (ESI): calcd. for C13H9BrClO2 ([M+H]+ ): 312.9448, found: 312.9458.
O Me
Me
OH
(2,6-Dimethylphenyl)(2-hydroxyphenyl)methanone (2ae)White solid, M.p. 112 – 113 ℃. 25.8 mg, 57%.1H NMR (300 MHz, CDCl3) δ 12.32 (s, 1H), 7.55 – 7.45 (m, 1H), 7.31 – 7.23 (m, 1H), 7.17 (dd, J = 8.0, 1.7 Hz, 1H), 7.12 – 7.04 (m, 3H), 6.83 – 6.75 (m, 1H), 2.16 (s, 6H).13C NMR (101 MHz, CDCl3) δ 206.6, 163.1, 138.3, 137.2, 134.2, 132.8, 129.3, 127.8, 120.2, 119.5, 118.5, 19.5.IR (KBr, ν / cm-1): 3069, 3000, 2955, 2924, 1623, 1576, 1489, 1449, 1328, 1306, 1243, 1224, 1151, 1030, 933, 827, 780, 766, 730, 690. HRMS (ESI): calcd. for C15H15O2 ([M+H]+ ): 227.1067, found: 227.1071.
OH
O OMe
(2-Hydroxyphenyl)(2-methoxyphenyl)methanone (2af)Colorless oil. 18.3 mg, 40%.1H NMR (300 MHz, CDCl3) δ 12.20 (s, 1H), 7.53 – 7.44 (m, 2H), 7.32 (ddd, J = 13.3, 7.7, 1.7 Hz, 2H), 7.11 – 6.98 (m, 3H), 6.87 – 6.75 (m, 1H), 3.78 (s, 3H).13C NMR (101 MHz, CDCl3) δ 202.3, 163.1, 156.7, 136.7, 134.0, 132.0, 129.0, 127.9, 120.7, 120.3, 118.9, 118.2, 111.6, 55.8.IR (KBr, ν / cm-1): 3013, 2955, 2840, 1628, 1600, 1487, 1461, 1332, 1310, 1280, 1246, 1148, 1121, 1023, 944, 980, 827, 754, 687. HRMS (ESI): calcd. for C14H13O3 ([M+H]+ ): 229.0859, found: 229.0865.
![Page 28: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/28.jpg)
28
O OMe
MeO
OH
(2,6-Dimethoxyphenyl)(2-hydroxyphenyl)methanone (2ag)White solid, M.p. 117 – 118 ℃. 20.1 mg, 39%.1H NMR (300 MHz, CDCl3) δ 12.16 (s, 1H), 7.50 – 7.43 (m, 1H), 7.38 (t, J = 8.4 Hz, 1H), 7.28 (dd, J = 8.0, 1.7 Hz, 1H), 7.02 (dd, J = 8.4, 1.0 Hz, 1H), 6.83 – 6.75 (m, 1H), 6.63 (d, J = 8.4 Hz, 2H), 3.73 (s, 6H).13C NMR (101 MHz, CDCl3) δ 201.5, 162.7, 157.5, 136.6, 133.2, 131.5, 121.1, 119.1, 118.1, 116.6, 104.1, 56.1.IR (KBr, ν / cm-1): 3011, 2963, 2842, 1630, 1593, 1474, 1448, 1332, 1306, 1254, 1220, 1146, 1112, 937, 758, 725, 678. HRMS (ESI): calcd. for C15H15O4 ([M+H]+ ): 259.0965, found: 259.0972.
![Page 29: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/29.jpg)
29
VII. References
1. D. Maiti and S. L. Buchwald, J. Org. Chem. 2010, 75, 1791–1794.2. H. Rao, X. Ma, Q. Liu, Z. Li, S. Cao, and C.-J. Li, Adv. Synth. Catal. 2013, 355,
2191–2196.3. D. C. Fabry, M. A. Ronge, J. Zoller, and M. Rueping, Angew. Chem. Int. Ed. 2015,
54, 2801–2805.4. D. Janssen-Müller, S. Singha, F. Lied, K. Gottschalk, F. Glorius, Angew. Chem. Int.
Ed. 2017, 56, 6276–6279.5. X. Qian, J. Han, L. Wang, RSC Adv. 2016, 6, 89234–89237.6. M. Pettersson, B. M. Campbell, A. B. Dounay, D. L. Gray, L. Xie, C. J. O’Donnell,
N. C. Stratman, K. Zoski, E. Drummond, G. Bora, A. Probert, T. Whisman, Bioorg. Med. Chem. Lett. 2011, 21, 865–868.
7. X. Yang, H. Wang, X. Zhou, X. Li, Org. Biomol. Chem., 2016, 14, 5233–5237.8. F. Weng, C. Wang, B. Xu, Tetrahedron Lett., 2010, 51, 2593-2596.
![Page 30: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/30.jpg)
30
VIII. Copies of the 1H, 19F and 13C NMR spectra
1H and 13C NMR spectra of compound 1a
-101234567891011121314f1 (ppm)
2.09
1.04
1.06
1.02
1.01
1.00
1.00
0.87
7.04
7.05
7.06
7.07
7.08
7.17
7.20
7.31
7.34
7.36
7.74
7.75
7.77
7.77
7.79
7.80
7.96
7.97
7.99
7.99
8.17
8.18
10.3
1
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
111.
9511
9.41
122.
6012
5.31
128.
6212
8.80
135.
7014
0.07
147.
87
156.
60
163.
52
189.
34
O
O
N
O
O
N
![Page 31: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/31.jpg)
31
1H and 13C NMR spectra of compound 1b
-101234567891011121314f1 (ppm)
3.00
1.08
1.00
1.11
2.19
2.10
0.85
2.41
6.95
6.97
6.99
7.14
7.17
7.28
7.31
7.33
7.57
7.60
7.62
7.62
7.65
7.96
7.96
7.98
7.98
10.3
010
.30
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
16.1
0
119.
5412
1.93
122.
5812
4.99
128.
4212
8.74
135.
5914
0.36
144.
90
156.
9316
1.77
189.
38
O
O
N
Me
O
O
N
Me
![Page 32: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/32.jpg)
32
1H and 13C NMR spectra of compound 1c
-101234567891011121314f1 (ppm)
3.00
2.08
1.03
0.97
1.03
2.04
1.00
2.39
6.87
6.89
7.14
7.14
7.17
7.17
7.28
7.31
7.33
7.60
7.62
7.64
7.95
7.97
8.02
8.04
10.3
110
.31
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
21.2
1
112.
1712
0.82
122.
4912
5.14
128.
5112
8.67
135.
68
147.
3615
1.75
156.
7916
3.76
189.
40O
O
N
Me
O
O
N
Me
![Page 33: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/33.jpg)
33
1H and 13C NMR spectra of compound 1d
-101234567891011121314f1 (ppm)
3.00
0.99
0.98
1.14
1.98
1.89
0.82
2.30
6.95
6.97
7.11
7.14
7.27
7.27
7.30
7.32
7.32
7.56
7.56
7.58
7.58
7.59
7.61
7.61
7.61
7.63
7.64
7.94
7.95
7.97
7.98
7.99
7.99
7.99
8.00
10.3
4
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
17.7
1
111.
57
122.
0712
4.96
128.
4012
8.69
128.
9313
5.69
140.
8914
7.56
157.
1516
1.62
189.
47O
O
NMe
O
O
NMe
![Page 34: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/34.jpg)
34
1H and 13C NMR spectra of compound 1e
-101234567891011121314f1 (ppm)
3.00
2.00
2.16
1.03
0.98
0.96
0.82
3.84
7.00
7.03
7.06
7.09
7.25
7.27
7.30
7.33
7.34
7.36
7.37
7.57
7.59
7.62
7.85
7.86
7.94
7.97
10.3
8
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
56.2
5
112.
8012
1.35
124.
6012
6.62
128.
0312
8.58
132.
8913
5.67
152.
9615
7.12
157.
67
189.
50
O
O
NOMe
O
O
NOMe
![Page 35: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/35.jpg)
35
1H and 13C NMR spectra of compound 1f
-101234567891011121314f1 (ppm)
3.00
2.02
0.99
1.03
2.07
0.97
0.86
3.69
6.48
6.49
6.49
6.51
6.51
6.51
7.17
7.18
7.20
7.20
7.31
7.59
7.61
7.64
7.95
7.95
7.97
10.3
410
.34
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
53.6
8
102.
1910
5.17
122.
5412
5.12
128.
2912
8.75
135.
5014
1.97
156.
8216
1.99
163.
40
189.
50
O
O
N
OMe
O
O
N
OMe
![Page 36: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/36.jpg)
36
1H and 13C NMR spectra of compound 1g
-101234567891011121314f1 (ppm)
1.00
0.99
1.06
1.03
1.05
2.03
1.00
7.05
7.06
7.08
7.09
7.13
7.13
7.16
7.16
7.32
7.32
7.32
7.34
7.37
7.37
7.37
7.49
7.50
7.51
7.52
7.52
7.53
7.54
7.55
7.61
7.62
7.64
7.64
7.64
7.64
7.66
7.67
7.96
7.96
7.98
7.99
8.00
8.01
10.3
010
.30
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
112.
8611
2.92
122.
3512
5.45
127.
5112
7.79
129.
1213
4.55
135.
76
146.
37
155.
0015
6.59
189.
22O
O
NF
O
O
NF
![Page 37: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/37.jpg)
37
19F NMR spectra of compound 1g
-250-240-230-220-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60f1 (ppm)
-134
.80
1H and 13C NMR spectra of compound 1h
-101234567891011121314f1 (ppm)
1.04
1.10
1.09
1.15
1.01
1.03
1.00
0.98
7.02
7.03
7.05
7.05
7.15
7.15
7.18
7.18
7.34
7.36
7.38
7.62
7.62
7.65
7.65
7.67
7.68
7.70
7.71
7.73
7.73
7.74
7.96
7.96
7.98
7.99
8.09
8.09
8.09
8.10
10.2
610
.26
O
O
NCl
![Page 38: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/38.jpg)
38
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
112.
87
122.
6612
5.71
126.
8412
8.63
129.
2713
5.75
139.
9014
6.20
156.
0216
1.91
189.
07
1H and 13C NMR spectra of compound 1i
-101234567891011121314f1 (ppm)
0.89
1.00
1.11
1.11
0.91
1.06
0.84
0.97
6.97
6.97
7.00
7.00
7.15
7.15
7.18
7.18
7.33
7.35
7.38
7.61
7.61
7.63
7.64
7.64
7.64
7.66
7.67
7.82
7.83
7.83
7.85
7.85
7.86
7.95
7.95
7.97
7.98
8.18
8.19
10.2
5
O
O
NCl
O
O
NBr
![Page 39: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/39.jpg)
39
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
113.
4411
4.57
122.
6812
5.72
128.
6912
9.30
135.
7014
2.58
148.
5115
5.94
162.
39
189.
00
1H and 13C NMR spectra of compound 1j
-101234567891011121314f1 (ppm)
2.00
1.00
1.05
2.00
1.00
0.88
7.17
7.20
7.20
7.23
7.23
7.23
7.39
7.42
7.44
7.66
7.66
7.68
7.69
7.69
7.71
7.71
7.96
7.97
7.98
7.99
8.00
8.00
8.39
8.40
8.40
8.40
10.2
0
O
O
NCF3
O
O
NBr
![Page 40: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/40.jpg)
40
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
111.
7712
2.76
123.
2012
6.25
128.
8012
9.81
135.
7913
7.35
145.
5314
5.56
155.
08
165.
66
188.
83
19F NMR spectra of compound 1j
-120-110-100-95-90-85-80-75-70-65-60-55-50-45-40-35-30-25-20-15-10-5051015f1 (ppm)
-61.
72
O
O
NCF3
![Page 41: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/41.jpg)
41
1H and 13C NMR spectra of compound 1k
-101234567891011121314f1 (ppm)
1.00
3.08
2.99
1.00
7.28
7.28
7.31
7.31
7.33
7.34
7.37
7.38
7.40
7.40
7.41
7.41
7.41
7.42
7.43
7.43
7.44
7.46
7.46
7.47
7.48
7.49
7.51
7.51
7.68
7.68
7.69
7.70
7.70
7.70
7.71
7.71
7.71
7.72
7.73
7.73
7.73
7.73
7.74
7.99
8.00
8.02
8.02
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
121.
6212
2.07
122.
1012
4.70
126.
6412
6.83
127.
8512
9.43
132.
5513
6.01
148.
75
156.
30
171.
40
188.
21O
O S
N
O
O S
N
![Page 42: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/42.jpg)
42
1H and 13C NMR spectra of compound 1l
-101234567891011121314f1 (ppm)
3.00
2.99
1.01
0.96
0.98
0.92
0.85
0.86
-0.0
0
2.30
2.64
7.15
7.15
7.17
7.18
7.32
7.33
7.33
7.35
7.37
7.38
7.38
7.60
7.61
7.63
7.63
7.63
7.64
7.66
7.66
7.95
7.96
7.98
7.98
8.07
10.2
510
.25
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
19.0
420
.65
122.
5812
5.41
128.
5212
9.20
135.
5213
8.01
141.
3614
8.71
155.
8815
7.31
189.
05O
ON
N
Me
Me
O
ON
N
Me
Me
![Page 43: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/43.jpg)
43
1H and 13C NMR spectra of compound 1m
-101234567891011121314f1 (ppm)
3.00
0.93
2.04
1.06
1.09
1.05
1.06
1.05
2.41
6.97
6.97
7.03
7.03
7.03
7.04
7.05
7.05
7.05
7.06
7.06
7.06
7.07
7.12
7.12
7.15
7.15
7.75
7.76
7.76
7.85
7.88
8.16
8.17
8.18
8.19
10.2
310
.23
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
22.1
0
111.
8711
9.24
122.
8712
6.23
126.
4112
8.72
139.
9914
7.30
147.
84
156.
52
163.
57
188.
99O
O
N
Me
O
O
N
Me
![Page 44: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/44.jpg)
44
1H and 13C NMR spectra of compound 1n
-101234567891011121314f1 (ppm)
3.00
2.00
0.97
0.99
0.98
0.92
0.87
0.90
2.17
6.97
6.99
6.99
6.99
7.00
7.01
7.01
7.02
7.02
7.04
7.05
7.05
7.30
7.53
7.53
7.71
7.71
7.73
7.74
7.74
7.74
7.80
8.08
8.08
8.09
8.10
8.10
10.1
510
.16
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
16.2
9
110.
5711
8.69
125.
9212
6.63
129.
5213
2.79
137.
5214
0.02
147.
8315
4.33
163.
66
189.
85O
O
N
Me
O
O
N
Me
![Page 45: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/45.jpg)
45
1H and 13C NMR spectra of compound 1o
-101234567891011121314f1 (ppm)
3.00
1.03
0.96
1.01
1.01
0.98
1.01
0.96
0.87
3.77
6.98
7.00
7.00
7.00
7.02
7.05
7.08
7.23
7.25
7.26
7.30
7.32
7.54
7.55
7.57
7.57
7.73
7.73
8.08
8.09
8.10
8.11
10.2
410
.24
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
56.3
7
110.
7111
8.23
118.
7911
9.62
126.
2113
0.30
139.
7514
5.47
147.
5715
2.47
163.
67
189.
68
O
O
N
OMe
O
O
N
OMe
![Page 46: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/46.jpg)
46
1H and 13C NMR spectra of compound 1p
-101234567891011121314f1 (ppm)
3.00
0.93
1.07
0.90
1.03
0.87
7.06
7.06
7.07
7.08
7.09
7.09
7.11
7.69
7.70
7.72
7.73
8.06
8.07
8.14
8.15
8.16
10.2
1
0102030405060708090100110120130140150160170180190200210220230240f1 (ppm)
111.
9911
8.57
119.
7412
4.68
130.
0213
1.39
138.
2414
0.24
147.
7915
5.47
163.
15
187.
86O
O
NBr
O
O
NBr
![Page 47: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/47.jpg)
47
1H and 13C NMR spectra of compound 1q
-101234567891011121314f1 (ppm)
2.04
1.00
1.03
0.98
1.02
1.00
0.99
7.04
7.04
7.06
7.06
7.07
7.08
7.09
7.17
7.18
7.20
7.21
7.30
7.32
7.33
7.33
7.34
7.34
7.36
7.37
7.61
7.62
7.63
7.65
7.74
7.75
7.77
7.77
7.77
7.78
7.79
7.80
8.13
8.13
8.14
8.14
8.15
8.15
8.16
10.2
110
.22
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
111.
7211
4.13
114.
4511
9.49
122.
5312
2.85
124.
7812
4.88
129.
8812
9.96
140.
1714
7.72
152.
3915
8.07
161.
3416
3.52
188.
18O
O
NF
O
O
NF
![Page 48: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/48.jpg)
48
19F NMR spectra of compound 1q
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)
-116
.11
1H and 13C NMR spectra of compound 1r
-101234567891011121314f1 (ppm)
2.09
1.00
1.03
1.04
0.97
1.00
0.89
7.05
7.06
7.06
7.07
7.07
7.08
7.08
7.09
7.09
7.14
7.17
7.55
7.55
7.55
7.56
7.57
7.58
7.58
7.59
7.75
7.75
7.75
7.76
7.77
7.78
7.78
7.80
7.80
7.81
7.91
7.92
8.14
8.14
8.15
8.16
8.16
8.16
10.2
310
.23
O
O
NCl
O
O
NF
![Page 49: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/49.jpg)
49
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
111.
9411
9.69
124.
3812
8.26
129.
6513
1.08
135.
3414
0.22
147.
7515
4.90
163.
21
187.
95
1H and 13C NMR spectra of compound 1s
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
16.3
0
56.2
8
110.
78
125.
7612
6.50
127.
2112
9.73
132.
2713
2.86
137.
51
152.
2715
4.84
158.
06
190.
01O
O
NCl
O
O
N
Me
OMe
![Page 50: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/50.jpg)
50
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
16.3
0
56.2
8
110.
78
125.
7612
6.50
127.
2112
9.73
132.
2713
2.86
137.
51
152.
2715
4.84
158.
06
190.
01
1H and 13C NMR spectra of compound 1t
-2-101234567891011121314f1 (ppm)
3.07
3.00
0.96
1.06
1.96
0.98
0.93
0.88
2.16
2.26
6.90
6.93
7.26
7.26
7.27
7.28
7.31
7.52
7.54
7.79
7.82
7.89
7.89
10.1
510
.15
O
O
N
Me
Me
O
O
N
Me
OMe
![Page 51: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/51.jpg)
51
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
16.2
917
.62
109.
86
125.
7912
6.52
127.
8812
9.63
132.
8313
7.50
140.
8614
7.38
154.
6216
2.04
189.
96
1H and 13C NMR spectra of compound 1u
-101234567891011121314f1 (ppm)
3.00
2.99
1.91
0.98
0.89
0.92
0.91
0.74
2.16
2.37
6.80
6.83
7.24
7.25
7.26
7.28
7.29
7.30
7.51
7.53
7.79
7.82
7.92
7.93
7.94
7.95
10.1
510
.15
O
O
N
Me
Me
O
O
N
MeMe
![Page 52: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/52.jpg)
52
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
16.2
321
.15
110.
59
120.
0612
5.74
126.
4012
9.47
132.
7413
7.42
147.
2415
1.57
154.
42
163.
93
189.
83
1H and 13C NMR spectra of compound 1v
-101234567891011121314f1 (ppm)
3.00
2.99
1.01
3.03
0.99
0.97
0.94
3.76
3.80
6.98
6.98
7.01
7.01
7.23
7.24
7.27
7.30
7.30
7.31
7.31
7.32
7.34
7.52
7.53
7.53
7.55
7.55
7.56
7.72
7.73
10.2
510
.26
O
O
N
MeMe
O
O
N
OMe
OMe
![Page 53: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/53.jpg)
53
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
56.2
456
.39
110.
9011
8.27
119.
5412
5.98
126.
8113
0.48
132.
08
146.
0215
2.36
152.
6015
8.03
189.
80
1H and 13C NMR spectra of compound 1w
-101234567891011121314f1 (ppm)
3.00
0.96
0.97
1.07
1.93
0.95
0.89
2.29
6.95
6.98
7.13
7.14
7.16
7.17
7.27
7.28
7.29
7.30
7.31
7.31
7.31
7.31
7.33
7.34
7.56
7.57
7.59
7.62
7.63
7.95
10.2
310
.24
O
O
N
OMe
OMe
O
O
NF Me
![Page 54: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/54.jpg)
54
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
17.6
4
111.
2311
3.97
114.
2912
2.48
122.
8012
4.36
124.
4612
8.96
129.
6812
9.76
140.
9614
7.34
152.
8915
7.87
161.
1416
1.68
188.
29
19F NMR spectra of compound 1w
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)
-116
.55
O
O
NF Me
O
O
NF Me
![Page 55: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/55.jpg)
55
1H and 13C NMR spectra of compound 1x
-101234567891011121314f1 (ppm)
3.18
2.28
1.12
1.06
0.99
1.02
1.00
0.96
7.31
7.34
7.37
7.39
7.40
7.42
7.65
7.66
7.67
7.68
7.68
7.69
7.70
7.70
7.71
7.72
7.72
7.75
7.75
7.78
7.78
7.80
7.80
7.84
7.86
7.93
7.95
8.01
8.02
8.04
8.04
8.46
8.49
10.2
9
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
117.
3811
9.58
123.
6312
4.10
125.
7912
6.67
127.
8012
8.97
129.
1613
1.41
135.
6813
8.85
139.
8015
6.46
160.
72
189.
19
O
O
N
O
O
N
![Page 56: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/56.jpg)
56
1H and 13C NMR spectra of compound 1y
-101234567891011121314f1 (ppm)
0.96
2.04
1.07
2.09
1.98
1.00
1.00
1.00
7.19
7.22
7.29
7.32
7.32
7.35
7.37
7.38
7.40
7.43
7.45
7.57
7.60
7.62
7.62
7.64
7.64
7.65
7.66
7.67
7.67
7.67
7.70
7.73
7.76
7.78
7.98
7.99
8.01
8.02
8.16
8.19
10.3
210
.32
0102030405060708090100110120130140150160170180190200210220230f1 (ppm)
112.
5612
3.08
125.
3812
5.42
127.
5712
8.02
128.
7113
0.17
135.
5114
0.49
156.
2516
1.60
189.
26O
O
N
O
O
N
![Page 57: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/57.jpg)
57
1H and 13C NMR spectra of compound 1z
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)
0.94
2.15
1.06
3.21
1.00
0.90
7.03
7.04
7.06
7.06
7.07
7.08
7.08
7.09
7.09
7.10
7.11
7.12
7.12
7.13
7.33
7.33
7.34
7.36
7.38
7.38
7.39
7.61
7.62
7.62
7.62
7.64
7.64
7.64
7.65
7.65
7.65
7.66
7.66
7.66
7.67
7.67
7.67
7.68
7.69
7.69
7.69
7.70
7.71
7.72
7.98
7.98
8.00
8.01
10.3
510
.36
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
107.
2611
8.64
119.
8512
0.66
125.
5612
7.97
129.
4613
4.59
136.
26
157.
3616
0.97
188.
57
O
O
CN
O
O
CN
![Page 58: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/58.jpg)
58
1H and 13C NMR spectra of compound 1aa
-101234567891011121314f1 (ppm)
3.00
3.14
1.09
1.01
1.01
2.08
0.86
3.91
7.00
7.03
7.05
7.06
7.08
7.08
7.29
7.29
7.32
7.57
7.58
7.60
7.63
7.96
7.96
7.98
7.99
8.05
8.06
8.07
8.08
8.09
10.4
110
.42
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
52.2
9
118.
0512
0.09
124.
7712
5.71
127.
6312
8.93
132.
0513
6.09
158.
3816
0.96
166.
40
188.
94
O
O
CO2Me
O
O
CO2Me
![Page 59: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/59.jpg)
59
1H and 13C NMR spectra of compound 1ab
-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)
1.00
1.98
1.09
3.01
0.95
0.89
6.98
7.00
7.11
7.14
7.28
7.30
7.32
7.57
7.58
7.59
7.61
7.62
7.63
7.65
7.97
7.97
7.99
7.99
10.4
2
0102030405060708090100110120130140150160170180190200210f1 (ppm)
118.
7211
9.96
122.
8012
5.50
126.
1412
6.47
127.
6512
7.68
127.
7212
7.76
127.
8012
9.19
136.
15
158.
5115
9.89
188.
93
O
O
CF3
O
O
CF3
![Page 60: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/60.jpg)
60
1H and 13C NMR spectra of compound 1ac
-101234567891011121314f1 (ppm)
1.00
5.18
1.07
1.00
0.84
6.77
6.80
7.13
7.14
7.15
7.16
7.16
7.17
7.18
7.18
7.19
7.20
7.20
7.21
7.22
7.22
7.23
7.23
7.24
7.24
7.25
7.46
7.47
7.49
7.49
7.49
7.50
7.51
7.52
7.93
7.93
7.95
7.96
10.6
110
.62
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
116.
3111
7.42
117.
6612
2.80
123.
3012
5.16
125.
2112
5.92
126.
1812
6.27
128.
6313
5.88
142.
5914
2.74
152.
8415
6.15
160.
10
189.
21
O
OF
O
OF
![Page 61: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/61.jpg)
61
1H and 13C NMR spectra of compound 1ad
-3-2-1012345678910111213141516f1 (ppm)
0.96
1.00
1.05
1.00
1.07
0.92
0.98
0.87
6.73
6.75
6.95
6.97
7.20
7.22
7.24
7.40
7.40
7.42
7.43
7.49
7.49
7.51
7.51
7.53
7.53
7.66
7.67
7.94
7.95
7.96
7.97
10.5
6
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
117.
0311
7.99
122.
9912
3.97
126.
4012
7.75
129.
0613
1.55
133.
8813
5.97
150.
96
159.
21
189.
00
O
OBr
Cl
O
OBr
Cl
![Page 62: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/62.jpg)
62
1H and 13C NMR spectra of compound 1ae
-101234567891011121314f1 (ppm)
6.00
1.06
1.15
3.06
1.09
1.06
0.93
2.15
6.43
6.45
7.07
7.09
7.09
7.12
7.13
7.13
7.37
7.39
7.40
7.92
7.92
7.94
7.95
10.7
810
.78
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
16.5
0
113.
6111
5.26
121.
7012
4.43
125.
8812
8.71
129.
3913
1.32
136.
13
150.
37
160.
32
189.
54O
OMe
Me
O
OMe
Me
![Page 63: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/63.jpg)
63
1H and 13C NMR spectra of compound 1af
-101234567891011121314f1 (ppm)
3.00
1.10
4.23
1.06
1.14
1.10
0.95
3.78
6.70
6.70
6.70
6.73
6.73
6.97
6.97
7.00
7.01
7.02
7.04
7.04
7.05
7.06
7.08
7.09
7.10
7.21
7.43
7.89
7.90
7.92
7.92
10.6
410
.65
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
55.9
0
112.
9811
6.34
121.
3212
2.10
122.
4612
5.58
126.
1512
8.14
135.
7214
3.79
151.
61
160.
96
189.
74O
OOMe
O
OOMe
![Page 64: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/64.jpg)
64
1H and 13C NMR spectra of compound 1ag
-101234567891011121314f1 (ppm)
6.00
3.15
1.05
1.04
1.05
1.00
0.86
3.77
6.62
6.62
6.65
6.65
6.68
7.02
7.05
7.07
7.15
7.18
7.21
7.35
7.36
7.38
7.38
7.38
7.39
7.40
7.41
7.87
7.88
7.90
7.90
10.7
710
.77
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
56.2
5
105.
3610
9.87
114.
9012
1.94
125.
0812
6.15
127.
8513
1.99
135.
59
153.
48
161.
46
190.
13
O
OOMe
OMe
O
OOMe
OMe
![Page 65: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/65.jpg)
65
1H and 13C NMR spectra of compound 2a
-101234567891011121314f1 (ppm)
1.00
0.96
1.97
1.93
0.96
0.94
0.85
6.88
6.88
6.90
6.90
6.91
6.93
6.93
7.04
7.04
7.07
7.07
7.48
7.49
7.49
7.50
7.51
7.51
7.51
7.52
7.52
7.52
7.53
7.54
7.54
7.89
7.90
7.92
7.93
7.93
7.94
7.94
7.95
7.96
8.10
8.10
8.12
8.13
8.72
8.73
8.73
8.74
8.74
8.75
12.3
6
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
118.
5911
9.01
119.
2612
4.75
126.
2813
4.45
136.
8213
7.60
148.
3715
5.41
163.
55
197.
35
OH
ON
OH
ON
![Page 66: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/66.jpg)
66
1H and 13C NMR spectra of compound 2b
-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)
3.00
1.08
1.02
2.10
1.07
1.04
0.98
0.88
2.37
6.80
6.80
6.83
6.85
6.85
7.04
7.05
7.07
7.07
7.33
7.33
7.35
7.36
7.38
7.48
7.48
7.50
7.50
7.51
7.66
7.69
8.51
8.51
8.53
8.53
12.0
8
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
18.1
9
118.
4311
9.13
119.
1812
4.81
131.
9813
3.72
137.
1513
9.16
146.
2415
4.41
163.
85
200.
64
OH
O
N
Me
OH
O
N
Me
![Page 67: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/67.jpg)
67
1H and 13C NMR spectra of compound 2c
-101234567891011121314f1 (ppm)
3.00
1.08
1.00
1.07
1.09
0.95
1.03
1.02
0.85
2.47
6.87
6.87
6.89
6.90
6.90
6.92
6.92
7.03
7.03
7.06
7.06
7.31
7.32
7.32
7.32
7.33
7.33
7.34
7.34
7.47
7.48
7.49
7.50
7.50
7.52
7.53
7.76
7.76
7.77
8.08
8.08
8.10
8.11
8.56
8.58
12.5
3
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
21.3
8
118.
6111
8.98
119.
6712
5.53
127.
2013
4.41
136.
68
148.
0214
9.21
155.
1716
3.26
197.
46
OH
ON
Me
OH
ON
Me
![Page 68: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/68.jpg)
68
1H and 13C NMR spectra of compound 2d
-101234567891011121314f1 (ppm)
3.02
1.00
0.93
1.01
1.00
0.96
0.96
0.92
0.83
2.45
6.87
6.87
6.89
6.90
6.92
6.92
7.03
7.03
7.03
7.05
7.06
7.06
7.46
7.47
7.49
7.49
7.50
7.70
7.70
7.70
7.71
7.72
7.72
7.73
7.73
7.86
7.89
8.16
8.16
8.18
8.19
8.54
8.54
8.54
8.54
12.5
1
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
18.8
1
118.
5611
8.91
119.
6212
4.58
134.
4213
6.54
137.
97
148.
6615
2.79
163.
29
196.
93
OH
ON
Me
OH
ON
Me
![Page 69: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/69.jpg)
69
1H and 13C NMR spectra of compound 2e
-101234567891011121314f1 (ppm)
3.00
1.09
1.03
1.09
1.07
1.03
1.03
0.96
0.95
6.88
6.91
6.93
7.02
7.05
7.34
7.34
7.36
7.37
7.46
7.49
7.51
8.01
8.04
8.30
8.32
8.38
8.39
12.4
6
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
55.9
9
118.
4211
8.83
119.
5012
0.64
126.
6613
4.54
136.
3313
6.38
147.
81
157.
8316
3.34
195.
79
OH
ON
OMe
OH
ON
OMe
![Page 70: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/70.jpg)
70
1H and 13C NMR spectra of compound 2f
-101234567891011121314f1 (ppm)
3.00
1.16
1.06
1.14
2.33
1.19
1.08
0.91
3.97
6.86
6.86
6.88
6.89
6.91
6.91
6.95
6.95
6.97
6.98
7.04
7.04
7.07
7.07
7.48
7.49
7.49
7.51
7.51
7.52
7.53
7.74
7.77
7.77
7.80
8.26
8.26
8.28
8.29
12.2
4
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
53.9
7
114.
3911
7.95
118.
4311
8.63
118.
94
134.
4313
6.68
139.
52
152.
82
162.
9516
4.00
197.
47
OH
ON OMe
OH
ON OMe
![Page 71: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/71.jpg)
71
1H and 13C NMR spectra of compound 2g
-101234567891011121314f1 (ppm)
1.09
1.02
1.07
1.07
1.04
1.01
1.00
0.98
6.89
6.92
6.94
7.04
7.07
7.50
7.52
7.55
7.59
7.60
7.62
7.63
7.64
7.65
8.00
8.02
8.03
8.05
8.16
8.16
8.19
8.58
8.58
12.1
2
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
118.
5111
8.64
119.
0012
4.06
124.
3012
6.75
126.
8213
4.46
136.
8613
6.97
137.
1815
1.70
158.
9516
2.44
163.
92
195.
96
OH
ON
F
OH
ON
F
![Page 72: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/72.jpg)
72
19F NMR spectra of compound 2g
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)
-120
.47
-120
.46
-120
.45
-120
.44
1H and 13C NMR spectra of compound 2h
-101234567891011121314f1 (ppm)
1.00
0.95
1.04
1.93
0.95
0.87
0.82
6.89
6.91
6.94
7.05
7.07
7.50
7.53
7.56
7.91
8.13
8.16
8.69
12.0
9
OH
ON
Cl
OH
ON
F
![Page 73: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/73.jpg)
73
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
118.
5411
9.04
125.
7613
4.34
135.
1713
7.11
137.
2614
7.48
153.
34
163.
94
196.
31
1H and 13C NMR spectra of compound 2i
-101234567891011121314f1 (ppm)
1.14
1.11
1.12
1.05
1.04
1.11
1.00
1.00
6.88
6.88
6.90
6.90
6.91
6.93
6.93
7.04
7.04
7.07
7.07
7.49
7.50
7.52
7.52
7.53
7.55
7.55
7.82
7.82
7.85
7.85
8.04
8.04
8.06
8.07
8.12
8.12
8.15
8.15
8.78
8.79
8.79
8.79
12.0
7
OH
ON
Cl
OH
ON
Br
![Page 74: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/74.jpg)
74
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
118.
5711
8.60
119.
0512
4.26
126.
0513
4.33
137.
1214
0.19
149.
6815
3.75
163.
98
196.
45
1H and 13C NMR spectra of compound 2j
-101234567891011121314f1 (ppm)
1.12
1.03
1.12
2.05
1.08
1.00
1.00
6.89
6.89
6.89
6.91
6.92
6.92
6.94
6.94
6.94
7.06
7.07
7.07
7.09
7.09
7.10
7.52
7.53
7.55
7.55
7.56
7.57
7.58
8.01
8.01
8.02
8.03
8.04
8.04
8.05
8.06
8.16
8.16
8.17
8.19
8.19
8.19
9.00
9.00
9.01
9.01
11.9
7
OH
ON
CF3
OH
ON
Br
![Page 75: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/75.jpg)
75
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
118.
4211
8.72
119.
2212
1.84
124.
3912
4.55
128.
4112
8.75
134.
3013
4.79
134.
8213
4.86
134.
8913
7.53
145.
5514
5.59
145.
6314
5.67
158.
4616
4.22
196.
49
19F NMR spectra of compound 2j
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)
-62.
59
OH
ON
CF3
OH
ON
CF3
![Page 76: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/76.jpg)
76
1H and 13C NMR spectra of compound 2k
-101234567891011121314f1 (ppm)
2.07
3.16
0.98
1.01
1.00
0.81
7.00
7.01
7.03
7.03
7.04
7.05
7.05
7.06
7.06
7.07
7.08
7.52
7.52
7.54
7.55
7.57
7.57
7.58
7.59
7.60
7.62
7.62
7.99
7.99
7.99
8.01
8.02
8.02
8.23
8.23
8.23
8.23
8.25
8.26
9.24
9.24
9.26
9.27
12.1
0
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
118.
2811
8.57
119.
7012
2.26
125.
8512
7.28
128.
0113
4.22
136.
8613
7.69
153.
81
164.
3116
7.24
187.
79
O
S
N
OH
O
S
N
OH
![Page 77: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/77.jpg)
77
1H and 13C NMR spectra of compound 2l
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)
3.00
2.94
0.97
0.92
0.89
0.98
0.87
0.81
2.55
2.60
6.83
6.83
6.85
6.85
6.86
6.88
6.88
7.06
7.07
7.09
7.10
7.27
7.28
7.29
7.31
7.31
7.51
7.52
7.54
7.54
7.55
8.52
11.9
3
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
21.1
721
.23
118.
7411
8.92
119.
34
133.
4813
7.69
144.
9614
8.61
148.
8115
0.10
164.
07
199.
40
OH
O
N
N Me
Me
OH
O
N
N Me
Me
![Page 78: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/78.jpg)
78
1H and 13C NMR spectra of compound 2m
-101234567891011121314f1 (ppm)
3.00
1.00
0.94
1.02
2.04
0.98
0.98
0.87
2.37
6.70
6.73
6.86
7.91
7.92
7.98
8.01
8.72
8.73
12.3
8
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
22.2
0
116.
8211
8.55
120.
4112
4.62
126.
0813
4.27
137.
47
148.
4014
8.65
155.
6216
3.87
196.
87
OH
ON
Me
OH
ON
Me
![Page 79: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/79.jpg)
79
1H and 13C NMR spectra of compound 2n
-101234567891011121314f1 (ppm)
3.14
1.08
1.05
1.03
3.09
1.00
0.92
2.31
6.77
6.80
6.83
7.37
7.39
7.46
7.46
7.47
7.47
7.48
7.48
7.49
7.49
7.50
7.50
7.51
7.88
7.88
7.89
7.90
7.91
8.71
8.72
8.73
8.73
12.5
3
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
15.8
5
118.
2311
8.33
124.
5512
6.01
127.
3913
2.03
137.
3713
7.63
148.
5015
5.71
162.
23
198.
08
OH
ON
Me
OH
ON
Me
![Page 80: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/80.jpg)
80
1H and 13C NMR spectra of compound 2o
-101234567891011121314f1 (ppm)
3.00
0.96
0.99
0.91
0.93
1.83
0.88
0.81
3.94
6.83
6.86
6.88
7.09
7.12
7.53
7.54
7.55
7.67
7.67
7.70
7.70
7.94
7.94
7.96
7.97
8.72
8.74
12.7
8
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
56.4
4
117.
3211
8.38
119.
8512
4.82
125.
4512
6.42
137.
74
148.
2214
9.24
153.
6915
5.34
197.
32
OH
ON
OMe
OH
ON
OMe
![Page 81: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/81.jpg)
81
1H and 13C NMR spectra of compound 2p
-101234567891011121314f1 (ppm)
1.00
2.03
2.09
0.96
0.97
0.79
6.94
6.97
7.55
7.55
7.56
7.58
7.58
7.58
7.59
7.96
7.96
7.98
7.99
8.00
8.01
8.01
8.01
8.37
8.38
8.74
8.74
12.6
3
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
110.
7312
0.78
121.
0512
5.12
126.
8613
6.39
138.
0113
9.27
148.
1615
4.59
162.
10
195.
26
OH
ONBr
OH
ONBr
![Page 82: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/82.jpg)
82
1H and 13C NMR spectra of compound 2q
-101234567891011121314f1 (ppm)
1.06
1.16
1.04
1.15
2.01
1.00
0.88
6.99
7.01
7.02
7.04
7.22
7.23
7.24
7.25
7.25
7.26
7.27
7.27
7.29
7.53
7.53
7.54
7.55
7.55
7.55
7.57
7.57
7.93
7.93
7.95
7.96
7.98
7.98
8.00
8.01
8.01
8.04
8.05
8.73
8.75
12.3
3
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
119.
0511
9.18
119.
3811
9.80
119.
8912
4.20
124.
5112
5.03
126.
7513
7.87
148.
1915
3.29
154.
7815
6.43
159.
63
195.
47
OH
ONF
OH
ONF
![Page 83: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/83.jpg)
83
19F NMR spectra of compound 2q
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)
-124
.33
-124
.32
-124
.31
-124
.30
-124
.30
-124
.29
-124
.28
1H and 13C NMR spectra of compound 2r
-101234567891011121314f1 (ppm)
1.01
1.01
1.04
2.08
0.95
1.00
0.87
7.00
7.03
7.43
7.43
7.45
7.46
7.54
7.54
7.56
7.56
7.57
7.58
7.58
7.94
7.94
7.96
7.96
7.97
7.99
7.99
8.01
8.01
8.01
8.03
8.23
8.24
8.74
8.75
12.6
0
OH
ONCl
OH
ONF
![Page 84: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/84.jpg)
84
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
120.
2912
0.34
123.
7012
5.10
126.
8513
3.37
136.
5313
7.99
148.
1715
4.58
161.
70
195.
42
1H and 13C NMR spectra of compound 2s
-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)
3.00
3.08
1.09
2.13
1.04
1.03
1.00
0.84
2.30
3.93
6.78
6.80
6.83
7.31
7.32
7.34
7.35
7.37
7.96
7.99
8.08
8.08
8.10
8.11
8.37
8.38
12.6
3
OH
ONCl
OH
ON
OMeMe
![Page 85: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/85.jpg)
85
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
15.9
0
55.9
3
118.
1211
8.48
120.
4312
6.46
127.
1713
2.12
136.
5013
7.15
148.
08
157.
6216
2.02
196.
54
1H and 13C NMR spectra of compound 2t
-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)
3.03
3.00
1.03
0.99
1.00
0.96
0.96
0.94
0.75
2.31
2.44
6.77
6.80
6.82
7.35
7.38
7.68
7.70
7.70
7.71
7.71
7.71
7.81
7.83
7.93
7.94
7.94
7.94
7.96
7.96
7.97
7.97
8.54
8.54
8.54
8.55
12.6
3
OH
ON
MeMe
OH
ON
OMeMe
![Page 86: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/86.jpg)
86
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
15.8
918
.79
118.
2411
8.48
124.
3912
7.30
132.
0313
6.51
137.
4013
7.72
148.
8615
3.07
162.
04
197.
81
1H and 13C NMR spectra of compound 2u
-101234567891011121314f1 (ppm)
3.00
3.00
1.01
0.95
0.96
0.95
0.96
0.96
0.78
2.31
2.46
6.77
6.79
6.82
7.29
7.29
7.29
7.30
7.30
7.31
7.36
7.36
7.38
7.70
7.70
7.71
7.86
7.86
7.87
7.89
7.89
8.56
8.57
12.6
2
OH
ON
MeMe
OH
ON
MeMe
![Page 87: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/87.jpg)
87
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
15.8
821
.33
118.
3111
8.53
125.
3412
6.93
127.
3613
2.03
137.
52
148.
2114
8.90
155.
5416
2.03
198.
31
1H and 13C NMR spectra of compound 2v
-101234567891011121314f1 (ppm)
3.00
3.05
1.04
1.05
1.03
1.07
1.07
0.99
0.91
3.93
3.96
6.83
6.86
6.88
7.08
7.10
7.28
7.35
7.36
7.38
7.39
7.85
7.86
7.88
7.89
8.03
8.06
8.37
8.38
12.8
3
OH
ON
MeMe
OH
ON
OMeOMe
![Page 88: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/88.jpg)
88
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
56.0
356
.38
116.
9111
8.14
120.
1012
0.77
125.
5812
6.72
136.
24
147.
8014
9.13
153.
4815
7.93
195.
78
1H and 13C NMR spectra of compound 2w
-101234567891011121314f1 (ppm)
3.00
0.99
1.12
1.02
1.00
0.97
0.97
0.82
2.47
6.98
6.99
7.01
7.02
7.20
7.21
7.23
7.23
7.23
7.24
7.24
7.26
7.27
7.73
7.74
7.74
7.76
7.76
7.76
7.76
7.95
7.97
8.05
8.06
8.08
8.09
8.55
8.55
8.55
12.5
2
OH
ON
OMeOMe
OH
ONF
Me
![Page 89: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/89.jpg)
89
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
18.8
7
119.
0511
9.38
119.
5111
9.60
119.
8111
9.91
123.
9512
4.27
124.
8913
7.51
138.
3014
8.50
152.
2115
3.34
156.
4815
9.35
195.
05
19F NMR spectra of compound 2w
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)
-124
.57
-124
.55
-124
.55
-124
.54
-124
.53
-124
.53
-124
.52
OH
ONF
Me
OH
ONF
Me
![Page 90: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/90.jpg)
90
1H and 13C NMR spectra of compound 2z
-101234567891011121314f1 (ppm)
1.00
0.93
0.97
1.02
1.94
1.90
0.90
6.88
6.88
6.90
6.90
6.91
6.93
6.93
7.09
7.09
7.12
7.12
7.44
7.44
7.46
7.47
7.53
7.54
7.56
7.56
7.57
7.58
7.59
7.75
7.75
7.75
7.76
7.77
7.78
7.81
7.82
7.83
7.84
7.84
11.7
9
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
115.
3311
7.86
118.
4911
8.79
119.
0612
9.43
132.
2013
3.02
137.
2114
1.55
163.
41
199.
72
OH
O
CN
OH
O
CN
![Page 91: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/91.jpg)
91
1H and 13C NMR spectra of compound 2aa
-101234567891011121314f1 (ppm)
3.00
1.09
0.99
2.15
2.04
2.05
0.92
3.98
6.89
6.89
7.08
7.08
7.08
7.10
7.10
7.10
7.11
7.50
7.50
7.50
7.51
7.53
7.53
7.53
7.71
7.72
7.72
7.74
7.74
7.74
8.16
8.16
8.17
8.18
8.19
8.19
11.9
3
-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)
52.6
9
118.
7611
9.05
129.
0912
9.73
133.
0313
3.53
137.
0114
1.79
163.
5016
6.35
167.
04
201.
09
OH
O
CO2Me
OH
O
CO2Me
![Page 92: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/92.jpg)
92
1H and 13C NMR spectra of compound 2ab
-101234567891011121314f1 (ppm)
1.00
0.96
2.00
3.77
0.84
6.87
6.88
6.90
6.90
6.90
6.92
6.93
7.09
7.09
7.12
7.12
7.49
7.49
7.52
7.52
7.53
7.53
7.55
7.55
7.56
7.58
7.58
7.79
11.8
9
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
118.
8811
8.94
119.
1512
2.43
124.
5512
5.14
125.
5812
5.61
125.
6512
5.69
129.
4713
3.42
133.
4713
3.75
137.
1814
1.21
163.
59
200.
60
OH
O
CF3
OH
O
CF3
![Page 93: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/93.jpg)
93
1H and 13C NMR spectra of compound 2ac
-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)
1.00
0.93
1.00
1.02
3.95
0.81
6.84
6.85
6.87
6.87
6.88
6.90
6.90
7.05
7.05
7.08
7.08
7.17
7.18
7.20
7.21
7.21
7.23
7.24
7.27
7.27
7.29
7.30
7.32
7.32
7.40
7.41
7.41
7.41
7.43
7.43
7.44
7.44
7.45
7.45
7.47
7.48
7.50
7.50
7.51
7.52
7.53
7.53
7.54
7.54
7.54
7.55
7.55
7.55
7.56
7.56
7.57
7.58
7.59
11.9
8
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
116.
3911
6.60
118.
4811
9.24
119.
9012
4.54
124.
5712
6.41
126.
5613
0.05
130.
0713
3.04
133.
1213
3.56
133.
5813
7.25
158.
0116
0.51
163.
20
198.
74
OH
O F
OH
O F
![Page 94: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/94.jpg)
94
19F NMR spectra of compound 2ac
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)
-112
.31
-112
.31
-112
.30
-112
.30
-112
.29
-112
.29
-112
.28
-112
.28
-112
.26
-112
.26
-112
.25
1H and 13C NMR spectra of compound 2ad
-3-2-1012345678910111213141516f1 (ppm)
1.00
0.95
1.86
1.97
0.86
0.85
6.82
6.82
6.84
6.84
6.84
6.86
6.86
7.06
7.06
7.08
7.08
7.21
7.21
7.22
7.23
7.23
7.24
7.51
7.51
7.52
7.53
7.53
7.53
7.54
7.55
7.56
7.67
7.68
11.8
3
OH
O F
O
OH
Br
Cl
![Page 95: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/95.jpg)
95
0102030405060708090100110120130140150160170180190200210f1 (ppm)
118.
7011
9.34
119.
4212
4.81
129.
8713
0.29
132.
2013
3.01
133.
4213
6.38
137.
64
163.
44
199.
68
1H and 13C NMR spectra of compound 2ae
-2-101234567891011121314f1 (ppm)
6.00
1.00
2.87
0.96
1.14
0.98
0.78
2.16
6.76
6.77
6.79
6.79
6.81
6.82
7.05
7.05
7.05
7.08
7.08
7.08
7.11
7.15
7.15
7.18
7.18
7.24
7.26
7.26
7.26
7.27
7.29
7.47
7.48
7.49
7.50
7.50
7.52
7.53
12.3
2
O Me
Me
OH
O
OH
Br
Cl
![Page 96: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/96.jpg)
96
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
19.5
3
118.
5111
9.54
120.
2312
7.78
129.
3313
2.82
134.
1513
7.23
138.
27
163.
10
206.
61
1H and 13C NMR spectra of compound 2af
-101234567891011121314f1 (ppm)
3.00
1.06
3.13
2.02
2.12
0.82
3.78
6.78
6.78
6.81
6.83
6.83
7.01
7.02
7.03
7.04
7.05
7.06
7.09
7.28
7.29
7.31
7.31
7.33
7.33
7.35
7.36
7.45
7.46
7.46
7.47
7.48
7.49
7.50
7.51
7.51
12.2
0
O Me
Me
OH
OH
O OMe
![Page 97: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/97.jpg)
97
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
55.8
3
111.
5611
8.23
118.
8812
0.33
120.
6612
7.88
129.
0013
2.03
133.
9513
6.68
156.
68
163.
05
202.
31
1H and 13C NMR spectra of compound 2ag
-101234567891011121314f1 (ppm)
6.00
1.96
0.99
0.93
0.92
1.01
0.98
0.74
3.73
6.62
6.65
6.76
6.76
6.79
6.81
6.81
7.01
7.01
7.03
7.04
7.27
7.27
7.30
7.30
7.35
7.38
7.41
7.43
7.44
7.46
7.47
7.48
7.49
12.1
6
O OMe
MeO
OH
OH
O OMe
![Page 98: Supporting Information3 iii. General procedures for preparation of starting material 1g Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde](https://reader033.vdocument.in/reader033/viewer/2022042918/5f5e25f0f555ee166210cd37/html5/thumbnails/98.jpg)
98
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
56.0
9
104.
12
116.
5511
8.05
119.
0712
1.14
131.
4913
3.21
136.
58
157.
4616
2.70
201.
49
O OMe
MeO
OH