substituted benzamides for synthesis of ...general procedure for the preparation of compounds 1. r 1...
TRANSCRIPT
S1
Supporting Information
Visible-Light-Induced Intramolecular sp3 C−H Oxidation of o-alkyl
Substituted Benzamides for Synthesis of IminoisobenzofuransLingang Wu, † Yanan Hao, † Yuxiu Liu, † and Qingmin Wang *,†,‡
†State Key Laboratory of Elemento-Organic Chemistry, Research Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, People’s Republic of China
‡Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300071,
People’s Republic of China
Table of Contents
1. Unsuccessful substrates (S2)
2. General procedure for the synthesis of substrate (S2-S8)
3. General procedure for the synthesis of products (S8-S14)
4. NMR spectra (S15-S58)
5. The X-ray crystallographic analysis data (S59-S67)
6. Analytical data of HRMS (S67-S70)
Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2019
S2
Unsuccessful substrates
O
NHBn
O
NH
CF3 O
NHPh
General procedure for the preparation of compounds 1.
R1NH2EDCI, DMAP
DCM, rt
O
OH
R3
R2R4
O
NHR1
R3
R2R4
A mixture of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (1.04g,
6.5 mmol, 1.3 equiv), DMAP (0.92g, 7.5 mmol, 1.5 equiv), acid (5 mmol, 1.0 equiv),
and amine (5 mmol, 1.0 equiv) in CH2Cl2 (20 mL) was stirred at room temperature for
6 h. After completing reaction, the mixture was added 30 mL H2O. The organic layer
was separated and the aqueous layer was extracted with dichloromethane (20mL × 3).
The combined organic phase was washed with brine (20 mL), and then dried over
Na2SO4. After filtration, the solvent was concentrated in vacuo. The products were
purified by column chromatography with petroleum ether and ethyl acetate as an
eluent.
2-isopropyl-N-phenylbenzamide (1a)
White solid. M.p. =132-134 °C. 1H NMR (400 MHz, CDCl3) δ 7.62
(d, J = 7.8 Hz, 2H), 7.49 (s, 1H), 7.47 – 7.33 (m, 5H), 7.28 – 7.21 (m,
1H), 7.19– 7.12(m, 1H), 3.48 – 3.35 (m, 1H), 1.28 (d, J = 6.9 Hz,
6H). 13C NMR (100 MHz, CDCl3) δ 168.5, 146.9, 138.0, 136.1, 130.4, 129.1, 126.4,
125.8, 124.6, 119.8, 30.0, 24.2. HRMS (ESI): calcd. for C16H18NO [M + H]+ 240.1383;
found 240.1381. (Petroleum ether/EtOAc, 5/1).
N-(4-bromophenyl)-2-isopropylbenzamide (1b)
White solid. M.p. =180-182 °C. 1H NMR (400 MHz, CDCl3)
δ 7.64 – 7.39 (m, 7H), 7.32 – 7.22 (m, 1H), 3.53 – 3.14 (m,
1H), 1.30 (d, J = 6.9 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ
168.5, 147.0, 137.1), 135.8, 132.1, 130.6, 126.4, 126.3,
125.8, 121.3, 117.1, 30.0, 24.1. HRMS (ESI): calcd. for C16H17BrNO [M + H]+
O
NHPh
1a
O
NH
1b
Br
S3
318.0488; found 318.0484. (Petroleum ether/EtOAc, 5/1).
N-(4-chlorophenyl)-2-isopropylbenzamide (1c)
White solid. M.p. =171-173 °C. 1H NMR (400 MHz, CDCl3)
δ 7.58 (t, J = 11.8 Hz, 3H), 7.47 – 7.35 (m, 3H), 7.31 (d, J =
8.4 Hz, 2H), 7.27 – 7.19 (m, 1H), 3.64 – 3.14 (m, 1H), 1.27 (d,
J = 6.8 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 168.5, 147.0,
136.6, 135.8, 130.6, 129.5, 129.1, 126.4, 126.3, 125.9, 121.0, 30.0, 24.1. HRMS (ESI):
calcd. for C16H17ClNO [M + H]+ 274.0993; found 274.0990. (Petroleum ether/EtOAc,
5/1).
N-(4-(tert-butyl)phenyl)-2-isopropylbenzamide (1d)
White solid. M.p. =148-150 °C. 1H NMR (400 MHz, CDCl3) δ
7.68 – 7.55(m, 2H), 7.53 – 7.39 (m, 6H), 7.32 – 7.22 (m, 1H),
3.60 – 3.21 (m, 1H), 1.36 (s, 9H), 1.31 (d, J = 6.9 Hz, 6H). 13C
NMR (100 MHz, CDCl3) δ 168.4, 147.6, 146.9, 136.2, 135.4,
130.3, 126.3, 126.3, 125.9, 125.8, 119.6, 34.4, 31.4, 30.0, 24.2. HRMS (ESI): calcd.
for C20H26NO [M + H]+ 296.2009; found 296.2005. (Petroleum ether/EtOAc, 5/1).
2-isopropyl-N-(p-tolyl)benzamide (1e)
White solid. M.p. =139-141 °C. 1H NMR (400 MHz,
CDCl3) δ 7.54 – 7.35 (m, 6H), 7.28 – 7.19 (m, 1H), 7.16
(d, J = 8.2 Hz, 2H), 3.48 – 3.31 (m, 1H), 2.34 (s, 3H),
1.27 (d, J = 6.9 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ
168.4, 146.9, 136.2, 135.4, 134.2, 130.3, 129.6, 126.4, 126.3, 125.8, 119.8, 30.0, 24.2,
20.9. HRMS (ESI): calcd. for C17H20NO [M + H]+ 254.1539; found 254.1536.
(Petroleum ether/EtOAc, 5/1).
N-([1,1'-biphenyl]-4-yl)-2-isopropylbenzamide (1f)
White solid. M.p. =184-186 °C. 1H NMR (400 MHz, CDCl3)
δ 7.74 (d, J = 8.1 Hz, 2H), 7.67 – 7.56 (m, 5H), 7.57 – 7.43
(m, 5H), 7.42 – 7.35 (m, 1H), 7.34-7.24 (m, 1H), 3.60 – 3.34
(m, 6.4 Hz, 1H), 1.34 (d, J = 6.7 Hz, 6H). 13C NMR (100
MHz, CDCl3) δ 168.5, 147.0, 140.5, 137.5, 137.3, 136.1, 130.5, 128.8, 127.7, 127.2,
O
NH
1c
Cl
O
NH
1d
tBu
O
NH
1e
Me
O
NH
1f
Ph
S4
126.9, 126.4, 125.8, 120.1, 30.0, 24.2. HRMS (ESI): calcd. for C22H22NO [M + H]+
316.1696; found 316.1691. (Petroleum ether/EtOAc, 5/1).
2-isopropyl-N-(m-tolyl)benzamide (1g)
White solid. M.p. =110-112 °C. 1H NMR (400 MHz, CDCl3)
δ 7.65 – 7.55 (m, 2H), 7.50 – 7.35 (m, 4H), 7.30 – 7.24 (m,
2H), 7.01 (d, J = 7.5 Hz, 1H), 3.77 – 3.10 (m, 1H), 2.40 (s,
3H), 1.31 (d, J = 6.9 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 168.5, 146.9, 139.1,
137.9, 136.2, 130.3, 128.9, 126.3, 126.3, 125.8, 125.3, 120.4, 116.8, 30.0, 24.2, 21.5.
HRMS (ESI): calcd. for C17H20NO [M + H]+ 254.1539; found 254.1536. (Petroleum
ether/EtOAc, 5/1).
2-isopropyl-N-(o-tolyl)benzamide (1h)
White solid. M.p. =126-127 °C. 1H NMR (400 MHz, CDCl3) δ
8.05 (d, J = 7.9 Hz, 1H), 7.55 – 7.40 (m, 3H), 7.39 – 7.19 (m,
4H), 7.20 – 7.08 (m, 1H), 3.57 – 3.42 (m, 1H), 2.33 (s, 3H), 1.33
(d, J = 6.8 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 168.5, 146.9,
130.6, 130.4, 128.9, 126.9, 126.4, 126.4, 125.8, 125.4, 122.9, 30.0, 24.2, 17.9. HRMS
(ESI): calcd. for C17H20NO [M + H]+ 254.1539; found 254.1535. (Petroleum
ether/EtOAc, 5/1).
N-(3,4-dichlorophenyl)-2-isopropylbenzamide (1i)
White solid. M.p. =118-120 °C. 1H NMR (400 MHz, CDCl3)
δ 7.89 (s, 1H), 7.68 – 7.56 (m, 1H), 7.48 – 7.33 (m, 5H), 7.25
– 7.13 (m, 1H), 3.43 – 3.26 (m, 1H), 1.27 (d, J = 6.7 Hz, 6H).
13C NMR (100 MHz, CDCl3) δ 168.5, 147.1, 137.4, 135.3,
132.9, 130.8, 130.5, 127.7, 126.5, 126.2, 125.8, 121.5, 119.0, 30.0, 24.1. HRMS (ESI):
calcd. for C16H16Cl2NO [M + H]+ 308.0603; found 308.0600. (Petroleum ether/EtOAc,
5/1).
2-isopropyl-N-(naphthalen-2-yl)benzamide (1j)
White solid. M.p. =156-158 °C. 1H NMR (400 MHz, CDCl3)
δ 8.37 (s, 1H), 7.88 – 7.76 (m, 3H), 7.65 (s, 1H), 7.53 – 7.38
(m, 6H), 7.30 – 7.21 (m, 1H), 3.52 – 3.40 (m, 1H), 1.31 (d, J
O
NH
1g
Me
O
NH
1h
Me
O
NH
1i
Cl
Cl
O
NH
1j
S5
= 6.8 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 168.6, 147.1, 136.1, 135.4, 133.9,
130.7, 130.5, 128.9, 127.7, 127.6, 126.6, 126.4, 125.8, 125.1, 119.7, 116.6, 30.1, 24.2.
HRMS (ESI): calcd. for C20H20NO [M + H]+ 290.1539; found 290.1534. (Petroleum
ether/EtOAc, 5/1).
2-isopropyl-N-methoxybenzamide (1k)
White solid. M.p. =122-124 °C. 1H NMR (400 MHz, CDCl3) δ 8.84
(s, 1H), 7.30 – 7.20 (m, 2H), 7.12 – 6.96 (m, 2H), 3.70 (s, 3H), 3.25
– 2.96 (m, 1H), 1.11 (d, J = 6.9 Hz, 6H). 13C NMR (100 MHz,
CDCl3) δ 168.1, 147.5, 132.1, 130.6, 127.0, 126.1, 125.5, 64.4, 29.9, 24.0. HRMS
(ESI): calcd. for C11H16NO2 [M + H]+ 194.1176; found 194.1172. (Petroleum
ether/EtOAc, 3/1).
2-cyclohexyl-N-phenylbenzamide (1l)
White solid. M.p. =120-122 °C. 1H NMR (400 MHz, CDCl3) δ 7.61
(d, J = 7.9 Hz, 2H), 7.53 (s, 1H), 7.44 – 7.30 (m, 5H), 7.26 – 7.13
(m, 2H), 3.08 – 2.92 (m, 1H), 1.98 – 1.65 (m, 5H), 1.51 – 1.20 (m,
5H). 13C NMR (100 MHz, CDCl3) δ 168.4, 145.9, 138.0, 136.3,
130.2, 129.1, 127.0, 126.5, 125.8, 124.5, 119.9, 40.5, 34.6, 26.7, 26.1. HRMS (ESI):
calcd. for C19H22NO [M + H]+ 280.1696; found 280.1691. (Petroleum ether/EtOAc,
5/1).
2-cyclopentyl-N-phenylbenzamide (1m)
White solid. M.p. =123-125 °C. 1H NMR (400 MHz, CDCl3) δ 7.64
(s, 1H), 7.59 (d, J = 7.8 Hz, 2H), 7.41 – 7.30 (m, 5H), 7.23 – 7.10
(m, 2H), 3.46 – 3.34 (m, 1H), 2.16 – 2.00 (m, 2H), 1.81 – 1.73 (m,
2H), 1.71 – 1.54 (m, 4H). 13C NMR (100 MHz, CDCl3) δ 168.7,
144.7, 138.0, 136.9, 130.3, 129.1, 126.9, 126.4, 125.7, 124.5, 119.8,
41.9, 35.3, 25.9. HRMS (ESI): calcd. for C18H20NO [M + H]+ 266.1539; found
266.1535. (Petroleum ether/EtOAc, 5/1).
tert-butyl-4-(2-(phenylcarbamoyl)phenyl)piperidine-1-
carboxylate (1n)
White solid. M.p. =210-212 °C. 1H NMR (400 MHz, CDCl3) δ
O
NHOMe
1k
O
NHPh
1l
O
NHPh
1m
O
NHPh
1n
NBoc
S6
7.66 – 7.51 (m, 3H), 7.48 – 7.30 (m, 5H), 7.29 – 7.22 (m, 1H), 7.19 – 7.11 (m, 1H),
4.24 – 4.08 (m, 2H), 3.26 – 3.12 (m, 1H), 2.83 – 2.64 (m, 2H), 1.89 – 1.81 (m, 2H),
1.64 – 1.57 (m, 2H), 1.45 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 168.0, 154.8, 144.3,
137.9, 136.2, 130.6, 129.2, 127.1, 126.6, 126.3, 124.7, 119.9, 79.4, 38.5, 33.3, 28.4.
HRMS (ESI): calcd. for C23H39N2O3 [M + H]+ 381.2173; found 381.2175. (Petroleum
ether/EtOAc, 5/1).
5-bromo-2-isopropyl-N-phenylbenzamide (1o)
White solid. M.p. =148-150 °C. 1H NMR (400 MHz, CDCl3) δ
7.72 – 7.50 (m, 5H), 7.44 – 7.35 (m, 2H), 7.33 – 7.28 (m, 1H),
7.23 – 7.16 (m, 1H), 3.42 – 3.30 (m, 1H), 1.28 (d, J = 6.6 Hz,
6H). 13C NMR (100 MHz, CDCl3) δ 166.7, 145.9, 137.8, 137.6,
133.3, 129.2, 129.1, 128.3, 124.8, 119.9, 119.2, 29.8, 24.0. HRMS (ESI): calcd. for
C16H17BrNO [M + H]+ 318.0488; found 318.0484. (Petroleum ether/EtOAc, 5/1).
2-cyclohexyl-5-fluoro-N-phenylbenzamide (1p)
White solid. M.p. =112-114 °C. 1H NMR (400 MHz, CDCl3) δ
7.81 – 7.63 (m, 1H), 7.58 – 7.38 (m, 2H), 7.27 – 7.14 (m, 3H),
7.08 – 6.86 (m, 3H), 2.92 – 2.74 (m, 1H), 1.87 – 1.49 (m, 5H),
1.42 – 0.92 (m, 5H). 13C NMR (100 MHz, CDCl3) δ 167.2,
160.30 (d, J = 246.3 Hz), 141.5, 137.7, 137.55 (d, J = 5.9 Hz),
129.1, 128.72 (d, J = 7.4 Hz), 124.7, 120.1, 117.03 (d, J = 20.5 Hz), 113.50 (d, J =
22.4 Hz), 40.0, 34.7, 26.7, 26.0. HRMS (ESI): calcd. for C19H21FNO [M + H]+
298.1602; found 298.1598. (Petroleum ether/EtOAc, 5/1).
5-bromo-2-cyclohexyl-N-phenylbenzamide (1q)
White solid. M.p. =132-133 °C. 1H NMR (400 MHz, CDCl3) δ
7.55 – 7.34 (m, 5H), 7.27 – 7.18 (m, 2H), 7.15 – 7.10 (m, 1H),
7.06 – 6.98 (m, 1H), 2.86 – 2.75 (m, 1H), 1.79 – 1.52 (m, 5H),
1.33 – 0.98 (m, 5H). 13C NMR (100 MHz, CDCl3) δ 166.7,
145.0, 138.0, 137.6, 133.2, 129.3, 129.2, 128.9, 124.8, 120.0, 119.1, 40.2, 34.4, 26.6,
26.0. HRMS (ESI): calcd. for C19H21BrNO [M + H]+ 358.0801; found 358.0797.
O
NHPh
1o
Br
O
NHPh
1p
F
O
NHPh
1q
Br
S7
2-cyclohexyl-5-methyl-N-phenylbenzamide (1r)
White solid. M.p. =108-110 °C. 1H NMR (400 MHz, CDCl3) δ
7.72 – 7.57 (m, 2H), 7.47 (s, 1H), 7.40 – 7.32 (m, 2H), 7.30 –
7.20 (m, 3H), 7.15 (t, J = 7.4 Hz, 1H), 3.01 – 2.90 (m, 1H), 2.34
(s, 3H), 1.92 – 1.59 (m, 5H), 1.51 – 1.10 (m, 5H). 13C NMR
(100 MHz, CDCl3) δ 168.5, 142.9, 138.0, 136.2, 135.4, 131.0, 129.1, 127.1, 126.9,
124.5, 119.8, 40.1, 34.7, 26.8, 26.1, 20.8. HRMS (ESI): calcd. for C20H24NO [M +
H]+ 294.1852; found 294.1850. (Petroleum ether/EtOAc, 5/1).
5-chloro-2-cyclohexyl-N-phenylbenzamide (1s)
White solid. M.p. =91-93 °C. 1H NMR (400 MHz, CDCl3) δ
7.62 – 7.49 (m, 3H), 7.42 – 7.27 (m, 5H), 7.19 – 7.09 (m,
1H), 3.15 – 2.58 (m, 1H), 1.92 – 1.66 (m, 5H), 1.45 – 1.18
(m, 5H). 13C NMR (100 MHz, CDCl3) δ 166.9, 144.4, 137.7,
137.6, 131.3, 130.2, 129.2, 128.6, 126.5, 124.8, 120.0, 40.1, 34.5, 26.6, 26.0. HRMS
(ESI): calcd. for C19H21ClNO [M + H]+ 314.1306; found 314.1302. (Petroleum
ether/EtOAc, 5/1).
4-chloro-2-cyclohexyl-N-phenylbenzamide (1t)
White solid. M.p. =187-189 °C. 1H NMR (400 MHz, CDCl3)
δ 7.65 – 7.50 (m, 3H), 7.41 – 7.24 (m, 4H), 7.20 – 7.07 (m,
2H), 3.11 – 2.82 (m, 1H), 1.88 – 1.63 (m, 5H), 1.47 – 1.13 (m,
5H). 13C NMR (100 MHz, CDCl3) δ 167.5, 148.2, 137.8,
136.3, 134.5, 129.1, 128.0, 127.4, 125.9, 124.7, 120.0, 40.4, 34.4, 26.6, 26.0. HRMS
(ESI): calcd. for C19H21ClNO [M + H]+ 314.1306; found 314.1303. (Petroleum
ether/EtOAc, 5/1).
2-ethyl-N-phenylbenzamide (1u)
White solid. M.p. =141-143 °C. 1H NMR (400 MHz, CDCl3) δ 7.80 –
7.50 (m, 3H), 7.43 – 7.29 (m, 5H), 7.25 – 7.18 (m, 1H), 7.16 – 7.07
(m, 1H), 2.97 – 2.74 (m, 2H), 1.32 – 1.08 (m, 3H). 13C NMR (100
MHz, CDCl3) δ 168.3, 142.5, 138.0, 136.2, 130.3, 129.6, 129.1, 126.6, 125.9, 124.5,
119.9, 26.3, 15.9. HRMS (ESI): calcd. for C15H16NO [M + H]+ 226.1226; found
O
NHPh
1r
Me
O
NHPh
1s
Cl
O
NHPh
1t
Cl
O
NHPh
1u
S8
226.1225. (Petroleum ether/EtOAc, 5/1).
2-methyl-N-phenylbenzamide (1v)
White solid. M.p. =125-127 °C. 1H NMR (400 MHz, CDCl3) δ 7.93
– 7.58 (m, 3H), 7.53 – 7.31 (m, 4H), 7.28 – 7.11 (m, 3H), 2.47 (s,
3H). 13C NMR (100 MHz, CDCl3) δ 168.3, 138.1, 136.4, 136.3,
131.2, 130.2, 129.0, 126.7, 125.8, 124.5, 120.0, 19.8. HRMS (ESI): calcd. for
C14H14NO [M + H]+ 212.1070; found 212.1073. (Petroleum ether/EtOAc, 5/1).
General experimental procedure for 2.
MeCN (2.5 mL), 48 hblue LED
O
N R1O
NHR1
R2R3 R
2
R3
Ru(bpy)3Cl26H2O (1.5 mol %)BI-OAc (1.5 equiv)
R4 R4
1 2
To a 10 mL glass vial was added 1 (0.25 mmol, 1.0 equiv), Ru(bpy)3Cl2•6H2O (2.8
mg, 0.00375 mmol, 1.5 mol %), BI-OAc (115 mg, 0.375 mmol, 1.5 equiv) and 2.5
mL of acetonitrile. The reaction mixture was degassed by bubbling with Ar for 15 s
with an outlet needle and the vial was sealed with PTFE cap. And the mixture was
stirred under the irradiation with blue LED for 48 h at room temperature. Upon
completion, the solvent was removed directly under reduced pressure to afford the
crude product, which was purified by flash column chromatography to afford the
desired product 2.
(Z)-3,3-dimethyl-N-phenylisobenzofuran-1(3H)-imine (2a)
White solid (48.0 mg, 81%). M.p. = 69-71 °C. 1H NMR (400
MHz, CDCl3) δ 7.93 (d, J = 7.6 Hz, 1H), 7.54 (td, J = 7.4, 0.9
Hz, 1H), 7.49 – 7.43 (m, 1H), 7.38 – 7.28 (m, 5H), 7.15 – 7.04
(m, 1H), 1.63 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 157.8,
151.5, 146.8, 131.9, 130.2, 128.6, 128.5, 124.0, 123.8, 123.6, 120.2, 88.2, 27.8.
HRMS (ESI): calcd. for C16H16NO [M + H]+ 238.1226; found 238.1223. (Petroleum
ether/EtOAc, 5/1).
(Z)-N-(4-bromophenyl)-3,3-dimethylisobenzofuran-
1(3H)-imine (2b)
White solid (61.2 mg, 82%). M.p. = 109-111 °C. 1H NMR
O
NHPh
1v
2a
O
N
2b
O
NBr
S9
(400 MHz, CDCl3) δ 7.90 (d, J = 7.6 Hz, 1H), 7.55 (td, J = 7.5, 1.0 Hz, 1H), 7.50 –
7.41 (m, 3H), 7.33 – 7.27 (m, 1H), 7.24 – 7.19 (m, 2H), 1.63 (s, 6H). 13C NMR (100
MHz, CDCl3) δ 158.3, 151.5, 145.8, 132.1, 131.5, 129.9, 128.7, 125.5, 124.0, 120.3,
116.7, 88.6, 27.8. HRMS (ESI): calcd. for C16H15BrNO [M + H]+ 316.0332; found
316.0330. (Petroleum ether/EtOAc, 5/1).
(Z)-N-(4-chlorophenyl)-3,3-dimethylisobenzofuran-1(3H)-
imine (2c)
White solid (47.5 mg, 70%). M.p. = 104-105 °C. 1H NMR
(400 MHz, CDCl3) δ 7.91 (d, J = 7.6 Hz, 1H), 7.56 (td, J = 7.5,
1.0 Hz, 1H), 7.47 (td, J = 7.5, 0.9 Hz, 1H), 7.34 – 7.24 (m,
5H), 1.72 – 1.50 (m, 6H). 13C NMR (100 MHz, CDCl3) δ 158.3, 151.5, 145.3, 132.1,
129.9, 128.9, 128.7, 128.6, 125.1, 124.0, 120.3, 88.6, 27.8. HRMS (ESI): calcd. for
C16H15ClNO [M + H]+ 272.0837; found 272.0834. (Petroleum ether/EtOAc, 5/1).
(Z)-N-(4-(tert-butyl)phenyl)-3,3-dimethylisobenzofuran-
1(3H)-imine (2d)
White solid (60.8 mg, 83%). M.p. = 78-80 °C. 1H NMR (400
MHz, CDCl3) δ 7.97 (d, J = 7.6 Hz, 1H), 7.57 (td, J = 7.4, 1.1
Hz, 1H), 7.49 (td, J = 7.5, 0.9 Hz, 1H), 7.44 – 7.36 (m, 4H),
7.34 – 7.32 (m, 1H), 1.68 (s, 6H), 1.38 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 157.4,
151.4, 146.6, 143.8, 131.7, 130.5, 128.6, 125.4, 124.0, 123.6, 120.2, 88.1, 34.4, 31.5,
27.9. HRMS (ESI): calcd. for C20H24NO [M + H]+ 294.1852; found 294.1849.
(Petroleum ether/EtOAc, 5/1).
(Z)-3,3-dimethyl-N-(p-tolyl)isobenzofuran-1(3H)-imine (2e)
Colourless oil (48.9 mg, 78%). 1H NMR (400 MHz, CDCl3) δ
7.92 (d, J = 7.6 Hz, 1H), 7.53 (td, J = 7.4, 1.0 Hz, 1H), 7.45
(td, J = 7.5, 0.8 Hz, 1H), 7.33 – 7.22 (m, 3H), 7.19 – 7.10 (m,
2H), 2.34 (s, 3H), 1.63 (s, 6H). 13C NMR (100 MHz, CDCl3) δ
157.6, 151.4, 144.1, 133.3, 131.8, 130.3, 129.2, 128.6, 123.9, 123.6, 120.2, 88.1, 27.9,
21.0. HRMS (ESI): calcd. for C17H18NO [M + H]+ 252.1383; found 252.1380.
(Petroleum ether/EtOAc, 5/1).
2c
O
NCl
2d
O
NtBu
2e
O
NMe
S10
(Z)-N-([1,1'-biphenyl]-4-yl)-3,3-dimethylisobenzofuran-
1(3H)-imine (2f)
White solid (50.1 mg, 64%). M.p. = 114-116 °C. 1H NMR
(400 MHz, CDCl3) δ 7.95 (d, J = 7.6 Hz, 1H), 7.67 – 7.58
(m, 4H), 7.55 (dt, J = 7.5, 3.7 Hz, 1H), 7.48 (td, J = 7.5, 1.0
Hz, 1H), 7.45 – 7.39 (m, 4H), 7.35 – 7.29 (m, 2H), 1.66 (s, 6H). 13C NMR (100 MHz,
CDCl3) δ 158.0, 151.5, 146.0, 141.1, 136.6, 131.9, 130.2, 128.7, 127.2, 126.8, 126.7,
124.2, 124.0, 120.2, 88.4, 27.8. HRMS (ESI): calcd. for C22H20NO [M + H]+ 314.1539;
found 314.1535. (Petroleum ether/EtOAc, 5/1).
(Z)-3,3-dimethyl-N-(m-tolyl)isobenzofuran-1(3H)-imine (2g)
Colourless oil (50.2 mg, 80%). 1H NMR (400 MHz, CDCl3) δ
7.92 (d, J = 7.6 Hz, 1H), 7.53 (td, J = 7.4, 0.8 Hz, 1H), 7.49 –
7.41 (m, 1H), 7.30 (d, J = 7.5 Hz, 1H), 7.27 – 7.19 (m, 1H),
7.16 – 7.07 (m, 2H), 6.98 – 6.88 (m, 1H), 2.36 (s, 3H), 1.63 (s,
6H). 13C NMR (101 MHz, CDCl3) δ 157.7, 151.5, 146.7, 138.2, 131.9, 130.2, 128.6,
128.3, 124.6, 124.3, 124.0, 120.4, 120.2, 88.1, 27.8, 21.5. HRMS (ESI): calcd. for
C17H18NO [M + H]+ 252.1383; found 252.1380. (Petroleum ether/EtOAc, 5/1).
(Z)-3,3-dimethyl-N-(m-tolyl)isobenzofuran-1(3H)-imine (2h)
Yellow oil (43.3 mg, 69%). 1H NMR (400 MHz, CDCl3) δ 7.95 (d,
J = 7.6 Hz, 1H), 7.55 (td, J = 7.4, 1.0 Hz, 1H), 7.48 (td, J = 7.5, 0.9
Hz, 1H), 7.31 (d, J = 7.5 Hz, 1H), 7.18 (dd, J = 16.9, 7.6 Hz, 2H),
7.12 – 7.05 (m, 1H), 7.01 (td, J = 7.4, 1.3 Hz, 1H), 2.25 (s, 3H),
1.60 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 157.0, 151.8, 146.2,
131.9, 130.1, 129.7, 128.6, 125.9, 124.0, 123.4, 121.6, 120.3, 87.8, 27.9, 18.1. HRMS
(ESI): calcd. for C17H18NO [M + H]+ 252.1383; found 252.1379. (Petroleum
ether/EtOAc, 5/1).
(Z)-N-(3,4-dichlorophenyl)-3,3-dimethylisobenzofuran-
1(3H)-imine (2i)
Colourless oil (56.6 mg, 74%). 1H NMR (400 MHz, CDCl3) δ
7.89 (d, J = 7.6 Hz, 1H), 7.57 (td, J = 7.5, 1.1 Hz, 1H), 7.52 –
2f
O
NPh
2g
O
NMe
2h
O
N
Me
2i
O
NCl
Cl
S11
7.44 (m, 2H), 7.37 (d, J = 8.6 Hz, 1H), 7.32 (d, J = 7.6 Hz, 1H), 7.18 (dd, J = 8.6, 2.4
Hz, 1H), 1.65 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 158.9, 151.6, 146.5, 132.4,
132.0, 130.1, 129.6, 128.8, 127.0, 125.6, 124.1, 123.6, 120.3, 89.1, 27.7. HRMS (ESI):
calcd. for C16H14Cl2NO [M + H]+ 306.0447; found 306.0443. (Petroleum ether/EtOAc,
5/1).
(Z)-3,3-dimethyl-N-(naphthalen-2-yl)isobenzofuran-
1(3H)-imine (2j)
Colourless oil (39.5 mg, 55%). 1H NMR (400 MHz, CDCl3)
δ 8.02 (d, J = 7.6 Hz, 1H), 7.85 (dd, J = 8.7, 4.4 Hz, 3H),
7.77 (d, J = 1.7 Hz, 1H), 7.63 – 7.51 (m, 3H), 7.49 – 7.39 (m,
2H), 7.36 (d, J = 7.5 Hz, 1H), 1.69 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 158.2,
151.6, 144.5, 134.1, 132.0, 130.8, 130.1, 128.7, 128.1, 127.6, 125.8, 124.5, 124.1,
124.1, 120.3, 120.2, 88.4, 27.8. HRMS (ESI): calcd. for C20H18NO [M + H]+ 288.1383;
found 288.1379. (Petroleum ether/EtOAc, 5/1).
(Z)-3,3-dimethylisobenzofuran-1(3H)-one O-methyl oxime (2k)
Colourless oil (40.1 mg, 84%). 1H NMR (400 MHz, CDCl3) δ 7.65
(d, J = 7.6 Hz, 1H), 7.46 (td, J = 7.5, 1.0 Hz, 1H), 7.38 (td, J = 7.6,
0.9 Hz, 1H), 7.30 – 7.21 (m, 1H), 3.96 (s, 3H), 1.67 (s, 6H). 13C
NMR (100 MHz, CDCl3) δ 155.3, 149.4, 130.8, 128.5, 127.4, 121.7,
120.4, 90.3, 62.7, 27.9. HRMS (ESI): calcd. for C11H14NO2 [M + H]+ 192.1019; found
192.1017. (Petroleum ether/EtOAc, 4/1).
(Z)-N-phenyl-3'H-spiro[cyclohexane-1,1'-isobenzofuran]-3'-imine
(2l)
Colourless oil (59.6 mg, 86%). 1H NMR (400 MHz, CDCl3) δ 7.95 (d,
J = 7.5 Hz, 1H), 7.52 (td, J = 7.4, 1.2 Hz, 1H), 7.48 – 7.42 (m, 3H),
7.40 – 7.32 (m, 2H), 7.30 (d, J = 7.4 Hz, 1H), 7.16 – 7.06 (m, 1H), 1.85
– 1.70 (m, 9H), 1.47 – 1.32 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 157.9, 151.3,
146.6, 131.6, 130.6, 128.7, 128.5, 124.2, 124.1, 123.9, 120.5, 89.6, 36.7, 24.9, 22.6.
HRMS (ESI): calcd. for C19H20NO [M + H]+ 278.1539; found 278.1537. (Petroleum
ether/EtOAc, 5/1).
2j
O
N
2k
O
N OMe
2l
O
N Ph
S12
(Z)-N-phenyl-3'H-spiro[cyclopentane-1,1'-isobenzofuran]-3'-imine
(2m)
Colourless oil (49.3 mg, 75%). 1H NMR (400 MHz, CDCl3) δ 7.93 (d,
J = 7.6 Hz, 1H), 7.55 (td, J = 7.5, 1.0 Hz, 1H), 7.46 (td, J = 7.5, 0.8
Hz, 1H), 7.40 – 7.30 (m, 5H), 7.15 – 7.06 (m, 1H), 2.19 – 1.84 (m,
8H). 13C NMR (100 MHz, CDCl3) δ 157.9, 149.3, 146.6, 131.9, 131.1, 128.6, 128.5,
123.9, 123.8, 123.7, 120.4, 98.2, 40.1, 25.0. HRMS (ESI): calcd. for C18H18NO [M +
H]+ 264.1383; found 264.1377. (Petroleum ether/EtOAc, 5/1).
tert-butyl (Z)-3-(phenylimino)-3H-spiro[isobenzofuran-1,4'-
piperidine]-1'-carboxylate (2n)
White solid (77.5 mg, 82%). M.p. = 170-172 °C. 1H NMR (400
MHz, CDCl3) δ 7.97 (d, J = 7.5 Hz, 1H), 7.53 (dt, J = 23.4, 7.4 Hz,
2H), 7.44 – 7.23 (m, 5H), 7.19 – 7.09 (m, 1H), 4.19 (s, 2H), 3.18 (s,
2H), 2.21 – 1.94 (m, 2H), 1.81 – 1.62 (m, 2H), 1.50 (s, 9H). 13C
NMR (100 MHz, CDCl3) δ 156.9, 154.7, 149.6, 146.2, 132.0, 130.6, 129.2, 128.6,
124.3, 124.2, 124.0, 120.5, 87.1, 79.9, 36.0, 28.4. HRMS (ESI): calcd. for
C23H27N2O3 [M + H]+ 379.2016; found 379.2012. (Petroleum ether/EtOAc, 5/1).
(Z)-6-bromo-3,3-dimethyl-N-phenylisobenzofuran-1(3H)-
imine (2o)
White solid (60.6 mg, 77%). M.p. = 80-82 °C. 1H NMR (400
MHz, CDCl3) δ 8.07 (d, J = 1.6 Hz, 1H), 7.65 (dd, J = 8.1, 1.7
Hz, 1H), 7.39 – 7.31 (m, 4H), 7.18 (d, J = 8.1 Hz, 1H), 7.15 – 7.07 (m, 1H), 1.63 (s,
6H). 13C NMR (100 MHz, CDCl3) δ 156.1, 150.1, 146.2, 134.8, 132.5, 128.6, 127.1,
124.2, 123.7, 122.6, 121.9, 88.3, 27.7. HRMS (ESI): calcd. for C16H15BrNO [M + H]+
316.0332; found 316.0328. (Petroleum ether/EtOAc, 5/1).
(Z)-5'-fluoro-N-phenyl-3'H-spiro[cyclohexane-1,1'-
isobenzofuran]-3'-imine (2p)
White solid (62.7 mg, 85%). M.p. = 102-104 °C. 1H NMR (400
MHz, CDCl3) δ 7.60 (dd, J = 8.0, 2.0 Hz, 1H), 7.45 (d, J = 7.4 Hz,
2H), 7.36 (t, J = 7.8 Hz, 2H), 7.29 – 7.18 (m, 2H), 7.12 (t, J = 7.3
2m
O
N Ph
2n
O
N Ph
NBoc
2o
O
N PhBr
2p
O
N PhF
S13
Hz, 1H), 1.85 – 1.65 (m, 9H), 1.45 – 1.32 (m, 1H). 13C NMR (100 MHz, CDCl3) δ
163.15 (d, J = 246.8 Hz), 156.6, 146.9, 146.1, 132.99 (d, J = 9.6 Hz), 128.6, 124.3,
124.2, 122.05 (d, J = 8.9 Hz), 119.31 (d, J = 24.0 Hz), 110.55 (d, J = 24.1 Hz), 89.6,
36.8, 24.8, 22.6. HRMS (ESI): calcd. for C19H19FNO [M + H]+ 296.1445; found
296.1441. (Petroleum ether/EtOAc, 5/1).
(Z)-5'-bromo-N-phenyl-3'H-spiro[cyclohexane-1,1'-
isobenzofuran]-3'-imine (2q)
White solid (65.0 mg, 73%). M.p. = 149-151 °C. 1H NMR (400
MHz, CDCl3) δ 8.09 (d, J = 1.6 Hz, 1H), 7.62 (dd, J = 8.1, 1.8 Hz,
1H), 7.48 – 7.42 (m, 2H), 7.39 – 7.32 (m, 2H), 7.20 – 7.09 (m,
2H), 1.90 – 1.64 (m, 9H), 1.43 – 1.33 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 156.2,
149.9, 146.0, 134.6, 132.9, 128.6, 127.1, 124.3, 124.3, 122.5, 122.1, 89.7, 36.6, 24.8,
22.5. HRMS (ESI): calcd. for C19H19BrNO [M + H]+ 356.0645; found 356.0641.
(Petroleum ether/EtOAc, 5/1).
(Z)-5'-methyl-N-phenyl-3'H-spiro[cyclohexane-1,1'-
isobenzofuran]-3'-imine (2r)
White solid (60.4 mg, 83%). M.p. = 77-79 °C. 1H NMR (400
MHz, CDCl3) δ 7.65 (s, 1H), 7.34 (dd, J = 8.4, 1.1 Hz, 2H),
7.27 – 7.19 (m, 3H), 7.08 (d, J = 7.7 Hz, 1H), 7.03 – 6.94 (m,
1H), 2.33 (s, 3H), 1.72 – 1.59 (m, 9H), 1.33 – 1.19 (m, 1H). 13C NMR (100 MHz,
CDCl3) δ 158.0, 148.8, 146.7, 138.7, 132.7, 130.8, 128.5, 124.3, 124.1, 123.8, 120.3,
89.5, 36.7, 24.9, 22.6, 21.2. HRMS (ESI): calcd. for C20H22NO [M + H]+ 292.1696;
found 292.1691. (Petroleum ether/EtOAc, 5/1).
(Z)-5'-chloro-N-phenyl-3'H-spiro[cyclohexane-1,1'-
isobenzofuran]-3'-imine (2r)
White solid (62.4 mg, 80%). M.p. = 154-156 °C. 1H NMR (400
MHz, CDCl3) δ 7.92 (s, 1H), 7.55 – 7.41 (m, 3H), 7.40 – 7.32 (m,
2H), 7.27 – 7.21 (m, 1H), 7.19 – 7.07 (m, 1H), 1.85 – 1.66 (m, 9H),
1.43 – 1.31 (m, 1H). 13C NMR (101 MHz, CDCl3) δ 156.3, 149.4, 146.1, 134.8, 132.7,
131.8, 128.6, 124.3, 124.2, 124.1, 121.8, 89.6, 36.6, 24.8, 22.5. HRMS (ESI): calcd.
2q
O
N PhBr
2s
O
N PhCl
2r
O
N PhMe
S14
for C19H19ClNO [M + H]+ 312.1150; found 312.1146. (Petroleum ether/EtOAc, 5/1).
(Z)-6'-chloro-N-phenyl-3'H-spiro[cyclohexane-1,1'-
isobenzofuran]-3'-imine (2t)
White solid (54.6 mg, 70%). M.p. = 92-94 °C. 1H NMR (400 MHz,
CDCl3) δ 7.87 (d, J = 8.2 Hz, 1H), 7.49 – 7.40 (m, 3H), 7.39 –
7.32 (m, 2H), 7.29 (d, J = 1.5 Hz, 1H), 7.16 – 7.08 (m, 1H), 1.85 –
1.65 (m, 9H), 1.46 – 1.31 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 156.6, 152.8, 146.2,
137.8, 129.3, 128.6, 125.4, 124.3, 124.1, 121.1, 89.2, 36.6, 24.8, 22.4. HRMS (ESI):
calcd. for C19H19ClNO [M + H]+ 312.1150; found 312.1144. (Petroleum ether/EtOAc,
5/1).
(Z)-3-methyl-N-phenylisobenzofuran-1(3H)-imine (2u)
White solid (22.3 mg, 40%). M.p. = 77-79 °C. 1H NMR (400 MHz,
CDCl3) δ 8.00 (d, J = 7.6 Hz, 1H), 7.60 (td, J = 7.4, 1.0 Hz, 1H),
7.53 (t, J = 7.4 Hz, 1H), 7.45 – 7.31 (m, 5H), 7.17 – 7.10 (m, 1H),
5.68 (q, J = 6.6 Hz, 1H), 1.64 (d, J = 6.6 Hz, 3H). 13C NMR (100
MHz, CDCl3) δ 158.5, 147.8, 146.7, 131.9, 130.6, 128.7, 128.6, 124.0, 123.9, 123.3,
121.0, 80.8, 21.0. HRMS (ESI): calcd. for C15H14NO [M + H]+ 224.1070; found
224.1067. (Petroleum ether/EtOAc, 5/1).
3,3-dimethylisobenzofuran-1(3H)-one (3)
White solid (32.4 mg, 80%). M.p. = 69-71°C. 1H NMR (400 MHz,
CDCl3) δ 7.93 – 7.79 (m, 1H), 7.74 – 7.65 (m, 1H), 7.52 (td, J = 7.5, 1.7
Hz, 1H), 7.45 (dd, J = 7.7, 1.8 Hz, 1H), 1.67 (s, 6H). 13C NMR (101
MHz, CDCl3) δ 169.8, 154.9, 134.1, 128.9, 125.6, 125.2, 120.7, 85.4, 27.3.
(Petroleum ether/EtOAc, 6/1).
NMR Spectra
2t
O
N Ph
Cl
2u
O
N Ph
3
O
O
S15
1H NMR spectrum of compound 1a
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
6.05
1.00
1.02
1.20
5.00
0.92
2.00
1.27
351.
2906
3.36
083.
3775
3.39
463.
4117
3.42
893.
4460
3.46
30
7.13
697.
1555
7.17
407.
2226
7.22
907.
2375
7.24
337.
2627
7.34
957.
3697
7.38
907.
4039
7.42
157.
4359
7.45
627.
4925
7.61
097.
6304
13C NMR spectrum of compound 1a
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
24.2
2
30.0
4
119.
8112
4.58
125.
8412
6.37
129.
1613
0.43
136.
1613
8.00
146.
96
168.
47
S16
1H NMR spectrum of compound 1b
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
5.96
1.02
1.07
7.13
1.29
361.
3107
3.35
023.
3676
3.38
473.
4018
3.41
893.
4359
3.45
29
7.24
737.
2523
7.26
777.
2825
7.29
137.
4080
7.42
747.
4380
7.45
547.
4751
7.47
887.
5012
7.53
767.
5596
7.60
13
13C NMR spectrum of compound 1b
-20-100102030405060708090100110120130140150160170180190200210f1 (ppm)
24.1
9
30.0
6
117.
1212
1.37
125.
8712
6.34
126.
4513
0.62
132.
0813
5.77
137.
09
147.
04
168.
47
S17
1H NMR spectrum of compound 1c
-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
6.17
1.10
1.25
1.97
3.10
3.00
1.26
121.
2783
3.32
143.
3376
3.35
453.
3715
3.38
863.
4057
3.42
21
7.21
617.
2331
7.25
917.
2983
7.31
937.
3726
7.39
157.
4053
7.42
387.
4393
7.45
947.
5500
7.57
117.
6088
13C NMR spectrum of compound 1c
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
24.1
9
30.0
5
121.
0612
5.86
126.
3412
6.43
129.
1212
9.51
130.
5913
5.77
136.
58
147.
02
168.
50
1H NMR spectrum of compound 1d
S18
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
6.06
8.96
1.07
1.16
5.97
2.05
1.29
991.
3170
1.36
16
3.39
303.
4100
3.42
723.
4443
3.46
143.
4785
3.49
56
7.24
807.
2547
7.26
267.
2680
7.27
267.
2821
7.29
097.
4147
7.41
987.
4363
7.44
677.
4611
7.48
137.
5106
7.57
397.
5954
13C NMR spectrum of compound 1d
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
24.2
230
.03
31.4
034
.45
119.
6412
5.82
125.
9712
6.32
126.
3913
0.34
135.
4013
6.29
146.
9014
7.62
168.
44
1H NMR spectrum of compound 1e
S19
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
6.21
3.05
1.08
2.00
1.04
6.09
1.26
351.
2806
2.33
85
3.35
213.
3692
3.38
633.
4035
3.42
063.
4377
3.45
48
7.15
277.
1732
7.20
627.
2131
7.22
057.
2262
7.23
147.
2401
7.24
657.
3830
7.40
707.
4136
7.42
147.
4416
7.44
427.
4857
7.50
661H NMR (400 MHz, CDCl3) δ3.48 – 3.31 (m, 1H).
13C NMR spectrum of compound 1e
-20-100102030405060708090100110120130140150160170180190200210f1 (ppm)
20.9
424
.22
30.0
3
119.
8912
5.81
126.
3212
6.40
129.
6213
0.34
134.
2513
5.47
136.
28
146.
92
168.
41
1H NMR spectrum of compound 1f
S20
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
6.32
1.05
1.23
1.11
5.00
4.89
2.01
1.32
691.
3435
3.43
903.
4549
3.47
143.
4883
3.50
46
7.29
177.
3642
7.38
207.
3999
7.48
007.
4995
7.56
267.
5832
7.62
287.
6329
7.65
237.
7320
7.75
21
13C NMR spectrum of compound 1f
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
24.2
4
30.0
8
120.
1512
5.88
126.
4112
6.92
127.
2212
7.78
128.
8513
0.50
136.
1113
7.30
137.
5114
0.51
147.
02
168.
52
1H NMR spectrum of compound 1g
S21
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
6.09
3.00
1.03
1.00
2.00
3.94
2.02
1.30
521.
3224
2.40
33
3.39
273.
4097
3.42
683.
4439
3.46
103.
4781
3.49
52
6.99
757.
0162
7.24
587.
2588
7.26
607.
2714
7.27
817.
2859
7.29
127.
2969
7.39
237.
4156
7.43
577.
4492
7.45
537.
4633
7.55
06
13C NMR spectrum of compound 1g
-100102030405060708090100110120130140150160170180190200210220f1 (ppm)
21.5
624
.24
30.0
4
116.
8812
0.45
125.
3912
5.83
126.
3512
6.39
128.
9613
0.39
136.
2513
7.96
139.
1414
6.93
168.
50
1H NMR spectrum of compound 1h
S22
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
6.11
3.00
1.07
1.00
4.00
3.01
0.94
1.32
641.
3434
2.32
94
3.44
103.
4481
3.46
483.
4818
3.49
883.
5158
3.53
263.
5491
3.55
53
7.10
067.
1165
7.14
197.
1604
7.17
887.
2562
7.27
627.
2919
7.31
247.
3319
7.47
127.
4788
7.49
948.
0384
8.05
83
13C NMR spectrum of compound 1h
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
17.9
324
.25
30.0
3
122.
9912
5.42
125.
8912
6.40
126.
4712
6.95
128.
9013
0.41
130.
6213
5.76
136.
2414
6.99
168.
57
1H NMR spectrum of compound 1i
S23
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
6.01
1.00
1.16
4.65
0.97
0.90
1.25
741.
2741
3.27
043.
2815
3.33
413.
3506
3.36
693.
4146
7.22
737.
2386
7.36
487.
3898
7.42
637.
4431
7.46
277.
5727
7.60
167.
6231
7.63
427.
6540
7.88
53
13C NMR spectrum of compound 1i
-20-100102030405060708090100110120130140150160170180190200210f1 (ppm)
24.1
8
30.0
5
119.
0012
1.50
125.
8912
6.29
126.
5112
7.72
130.
5813
0.80
132.
9313
5.36
137.
4314
7.12
168.
52
1H NMR spectrum of compound 1j
S24
-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
5.99
1.09
1.25
6.06
1.00
3.02
1.00
1.29
661.
3137
3.41
113.
4281
3.44
513.
4622
3.47
933.
4963
3.51
22
7.24
587.
2529
7.26
587.
2782
7.28
527.
4034
7.42
127.
4431
7.45
657.
4765
7.49
697.
5144
7.51
857.
6475
7.78
997.
8149
7.83
758.
3748
13C NMR spectrum of compound 1j
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
24.2
6
30.1
0
116.
6011
9.70
125.
1812
5.89
126.
4512
6.66
127.
6112
7.78
128.
9413
0.54
130.
7813
3.90
135.
4213
6.12
147.
10
168.
63
1H NMR spectrum of compound 1k
S25
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
6.18
1.02
3.08
2.01
2.04
0.97
1.09
671.
1138
3.08
263.
0891
3.14
243.
1576
3.17
28
3.70
19
7.00
717.
0102
7.02
597.
0423
7.08
917.
1071
7.22
017.
2400
7.24
557.
2630
7.26
607.
2825
7.28
58
8.83
93
13C NMR spectrum of compound 1k
-20-100102030405060708090100110120130140150160170180190200210f1 (ppm)
24.0
8
29.9
4
64.4
6
125.
5612
6.12
127.
0813
0.68
132.
14
147.
53
168.
10
1H NMR spectrum of compound 1l
S26
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
5.31
5.03
1.02
2.09
5.05
0.99
2.00
1.22
351.
2544
1.28
481.
3270
1.35
811.
3898
1.41
581.
4414
1.47
431.
5010
1.50
521.
7071
1.73
841.
7797
1.81
041.
8803
1.90
992.
9413
2.96
812.
9753
2.98
282.
9966
3.00
393.
0253
3.03
24
7.13
337.
1518
7.17
027.
2041
7.21
847.
2381
7.24
907.
3167
7.34
507.
3649
7.39
207.
4082
7.42
827.
5316
7.59
577.
6153
13C NMR spectrum of compound 1l
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
26.1
526
.79
34.6
1
40.5
3
119.
9212
4.55
125.
8012
6.58
127.
0312
9.16
130.
2913
6.33
138.
0614
5.96
168.
48
1H NMR spectrum of compound 1m
S27
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
4.17
2.01
2.00
1.00
1.96
5.07
2.01
1.10
1.55
281.
5749
1.59
231.
5985
1.62
591.
6332
1.63
831.
6505
1.65
751.
6671
1.68
951.
6988
1.73
751.
7469
1.78
291.
7894
1.79
552.
0473
2.06
792.
0722
2.08
722.
0949
3.35
863.
3799
3.40
013.
4194
3.44
25
7.11
627.
1346
7.15
317.
1720
7.18
257.
1923
7.20
187.
2123
7.22
237.
3206
7.34
097.
3532
7.35
987.
3713
7.39
047.
4001
7.58
277.
6022
7.64
21
13C NMR spectrum of compound 1m
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
25.9
0
35.3
1
41.9
5
119.
8612
4.54
125.
7112
6.40
126.
9212
9.15
130.
3513
6.98
138.
0714
4.76
168.
76
S28
1H NMR spectrum of compound 1n
-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
9.01
2.23
2.00
2.14
1.04
2.04
1.00
1.33
5.00
3.00
1.44
761.
5775
1.60
701.
6210
1.65
081.
7814
1.81
831.
8494
1.88
252.
6954
2.76
832.
7803
2.79
093.
1659
3.19
633.
2191
3.22
58
4.13
234.
1554
4.17
724.
1944
4.22
74
7.11
467.
1335
7.15
207.
1704
7.18
597.
2400
7.25
847.
2768
7.30
667.
3291
7.34
707.
3654
7.38
487.
4048
7.42
467.
4303
7.44
957.
5468
7.58
667.
6062
7.63
597.
6471
13C NMR spectrum of compound 1n
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
28.4
933
.30
38.5
9
79.4
3
119.
9312
4.74
126.
3312
6.65
127.
1012
9.22
130.
6213
6.22
137.
9214
4.33
154.
85
168.
06
1H NMR spectrum of compound 1o
S29
-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
6.00
1.04
1.00
1.12
2.01
4.95
1.27
371.
2903
3.32
923.
3444
3.36
093.
3775
3.39
383.
3938
3.40
89
7.16
137.
1830
7.20
047.
2186
7.21
867.
2912
7.30
437.
3043
7.32
647.
3605
7.38
527.
4039
7.42
227.
4222
7.50
737.
5150
7.52
647.
5715
7.57
157.
6297
7.64
877.
6487
7.68
657.
6889
13C NMR spectrum of compound 1o
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
24.0
5
29.8
1
119.
2311
9.96
124.
8812
8.31
129.
1912
9.23
133.
3713
7.67
137.
8914
5.99
166.
77
1H NMR spectrum of compound 1p
S30
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)
5.01
5.02
1.01
3.00
2.99
2.01
1.02
1.10
511.
1305
1.15
921.
1884
1.21
921.
2493
1.27
511.
3038
1.33
211.
5961
1.61
881.
6254
1.66
001.
6848
1.72
641.
7493
2.75
722.
8211
2.91
172.
9192
6.90
736.
9286
6.96
616.
9858
7.03
457.
0516
7.06
917.
1476
7.22
177.
2400
7.25
717.
3875
7.39
067.
4611
7.47
977.
5738
7.67
817.
7048
7.70
827.
7639
7.79
52
13C NMR spectrum of compound 1p
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
26.0
626
.74
34.7
3
40.0
4
113.
3811
3.61
116.
9311
7.14
120.
1212
4.78
128.
6912
8.76
129.
1413
7.52
137.
5813
7.78
141.
59
159.
0816
1.53
167.
23
1H NMR spectrum of compound 1q
S31
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
5.09
5.00
1.00
1.00
1.04
2.02
4.93
1.04
741.
0702
1.07
811.
1011
1.13
191.
1719
1.20
311.
2321
1.25
751.
2875
1.31
751.
5667
1.59
771.
6376
1.66
171.
7147
1.73
922.
7766
2.79
742.
8044
2.82
522.
8316
6.97
926.
9940
7.01
737.
0358
7.05
437.
1117
7.11
977.
1318
7.18
897.
2200
7.24
007.
2590
7.37
157.
3920
7.45
007.
4695
13C NMR spectrum of compound 1q
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
26.0
226
.66
34.4
8
40.2
0
119.
1912
0.02
124.
8612
8.96
129.
2212
9.38
133.
2513
7.69
138.
0014
5.01
166.
78
1H NMR spectrum of compound 1r
S32
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
5.20
5.05
3.01
1.01
1.00
3.01
1.91
1.02
2.00
1.19
131.
2145
1.24
511.
2532
1.27
571.
2840
1.31
901.
3503
1.38
201.
4027
1.42
501.
4578
1.48
851.
6178
1.69
911.
7304
1.77
181.
8019
1.86
151.
8902
2.33
76
2.92
922.
9504
2.95
742.
9786
2.98
57
7.09
017.
1000
7.13
237.
1507
7.16
917.
2143
7.22
957.
2500
7.26
857.
2898
7.34
797.
3677
7.38
697.
4726
7.59
697.
6164
13C NMR spectrum of compound 1r
-100102030405060708090100110120130140150160170180190200f1 (ppm)
20.8
626
.17
26.8
3
34.7
2
40.1
7
119.
8712
4.51
126.
9712
7.14
129.
1613
1.01
135.
4313
6.22
138.
0914
2.93
168.
58
1H NMR spectrum of compound 1s
S33
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
5.31
5.04
1.01
1.00
5.00
3.00
1.20
461.
2122
1.23
521.
2652
1.28
631.
3034
1.33
481.
3638
1.38
891.
4183
1.70
091.
7320
1.77
031.
7991
1.84
261.
8672
2.89
312.
9166
2.92
352.
9378
2.94
462.
9657
2.97
202.
9923
7.14
867.
1670
7.18
557.
2951
7.30
607.
3177
7.35
187.
3572
7.36
827.
3867
7.58
117.
6003
13C NMR spectrum of compound 1s
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
26.0
426
.68
34.5
4
40.1
5
120.
0512
4.84
126.
5512
8.61
129.
2013
0.27
131.
3413
7.66
137.
7314
4.47
166.
96
1H NMR spectrum of compound 1t
S34
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
5.03
5.11
1.00
2.00
4.23
3.00
1.20
981.
2392
1.26
451.
2945
1.32
661.
3563
1.38
061.
4102
1.44
021.
6492
1.69
921.
7302
1.77
251.
7960
1.84
521.
8679
2.97
463.
0007
7.15
797.
1755
7.24
697.
2549
7.28
597.
2931
7.30
627.
3136
7.33
787.
3563
7.37
327.
5753
7.59
067.
6234
13C NMR spectrum of compound 1t
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
26.0
026
.63
34.4
2
40.4
6
120.
0112
4.78
125.
9212
7.43
128.
0112
9.19
134.
5813
6.30
137.
82
148.
21
167.
56
1H NMR spectrum of compound 1u
S35
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
3.11
2.06
1.00
1.07
5.03
3.00
1.21
741.
2212
1.23
621.
2400
1.24
841.
2549
1.25
87
2.81
212.
8304
2.84
31
7.11
357.
1312
7.14
977.
1930
7.21
107.
2285
7.23
607.
2426
7.27
277.
2916
7.31
757.
3358
7.35
507.
3746
7.39
087.
4077
7.58
137.
6000
7.69
27
13C NMR spectrum of compound 1u
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
15.9
4
26.3
9
119.
9612
4.56
125.
9012
6.67
129.
1212
9.67
130.
3913
6.24
138.
0614
2.58
168.
38
1H NMR spectrum of compound 1v
S36
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
3.00
3.00
4.00
3.01
2.47
26
7.15
257.
1696
7.18
797.
2187
7.23
997.
2586
7.36
197.
4144
7.43
137.
6231
7.64
027.
8946
13C NMR spectrum of compound 1v
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
19.8
2
120.
0112
4.52
125.
8512
6.71
129.
0713
0.22
131.
2013
6.34
136.
4413
8.10
168.
31
S37
1H NMR spectrum of compound 2a
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
6.01
1.01
5.03
1.04
1.00
0.97
1.63
19
7.05
227.
0728
7.07
907.
0865
7.09
427.
1004
7.10
837.
1139
7.12
187.
1332
7.14
317.
2968
7.31
577.
3336
7.34
197.
3467
7.36
217.
3685
7.43
347.
4477
7.46
457.
4661
7.48
317.
4850
7.52
207.
5244
7.54
077.
5430
7.55
927.
5615
7.92
527.
9442
13C NMR spectrum of compound 2a
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
27.8
4
88.2
6
120.
2812
3.67
123.
8612
4.04
128.
5912
8.67
130.
2013
1.95
146.
8115
1.57
157.
88
S38
1H NMR spectrum of compound 2b
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
6.00
1.91
1.15
2.99
1.00
0.99
1.63
43
7.19
847.
2057
7.21
077.
2223
7.22
757.
2346
7.28
497.
3026
7.32
157.
4179
7.42
517.
4302
7.44
187.
4469
7.46
797.
4699
7.48
657.
4888
7.53
427.
5368
7.55
297.
5554
7.57
157.
5740
7.89
497.
9139
13C NMR spectrum of compound 2b
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
27.8
1
88.6
6
116.
7912
0.33
124.
0512
5.55
128.
7612
9.94
131.
5913
2.18
145.
89
151.
57
158.
33
S39
1H NMR spectrum of compound 2c
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
6.00
5.06
1.04
1.00
0.99
1.63
96
7.25
827.
2697
7.28
577.
3061
7.32
497.
4522
7.45
437.
4708
7.47
287.
4895
7.49
177.
5358
7.53
857.
5545
7.55
717.
5731
7.57
567.
8971
7.91
62
13C NMR spectrum of compound 2c
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
27.8
2
88.6
2
120.
3112
4.04
125.
1312
8.63
128.
7512
8.95
129.
9613
2.14
145.
37
151.
55
158.
30
S40
1H NMR spectrum of compound 2d
-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
9.18
6.00
1.00
4.14
1.04
1.03
0.98
1.38
26
1.68
26
7.33
137.
3500
7.37
137.
3729
7.37
857.
3869
7.39
397.
4015
7.40
857.
4168
7.42
237.
4241
7.47
347.
4756
7.49
197.
4941
7.51
057.
5129
7.54
557.
5482
7.56
417.
5668
7.58
267.
5852
7.96
377.
9826
13C NMR spectrum of compound 2d
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
27.9
531
.52
34.4
0
88.1
3
120.
2512
3.62
124.
0312
5.44
128.
6113
0.52
131.
77
143.
8714
6.66
151.
4115
7.42
S41
1H NMR spectrum of compound 2e
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
6.09
3.15
2.16
3.00
1.09
1.18
1.02
1.62
72
2.34
10
7.13
597.
1564
7.17
957.
2494
7.27
027.
2862
7.30
497.
4327
7.43
477.
4513
7.45
327.
4699
7.47
207.
5064
7.50
917.
5251
7.52
767.
5436
7.54
607.
9130
7.93
20
13C NMR spectrum of compound 2e
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
21.0
8
27.9
0
88.1
4
120.
2712
3.65
123.
9712
8.63
129.
2313
0.34
131.
8213
3.36
144.
10
151.
49
157.
62
S42
1H NMR spectrum of compound 2f
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
6.01
2.01
4.09
1.15
1.05
4.17
1.00
1.66
44
7.29
197.
2947
7.29
767.
3130
7.33
167.
3897
7.40
957.
4273
7.44
337.
4482
7.46
027.
4626
7.47
897.
4812
7.49
767.
5001
7.53
437.
5371
7.55
297.
5557
7.57
157.
5742
7.57
907.
5849
7.58
997.
6014
7.60
637.
6125
7.61
787.
6202
7.63
327.
6379
7.64
137.
6552
7.65
757.
9426
7.96
15
13C NMR spectrum of compound 2f
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
27.8
9
88.4
4
120.
2912
4.08
124.
2412
6.79
126.
8812
7.29
128.
7013
0.25
131.
9813
6.63
141.
1314
6.07
151.
5615
8.00
S43
1H NMR spectrum of compound 2g
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
6.03
3.04
1.01
1.94
1.17
1.03
1.01
1.00
0.96
1.62
73
2.36
10
6.90
786.
9263
6.94
496.
9641
6.97
947.
0805
7.10
087.
1208
7.13
497.
1555
7.19
437.
2097
7.22
877.
2448
7.24
747.
2690
7.28
817.
3069
7.42
867.
4379
7.45
517.
4736
7.51
227.
5145
7.53
097.
5330
7.54
947.
5513
7.91
267.
9316
13C NMR spectrum of compound 2g
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
21.5
5
27.8
6
88.1
8
120.
2712
0.46
124.
0112
4.37
124.
6712
8.39
128.
6413
0.25
131.
9013
8.25
146.
7515
1.58
157.
72
S44
1H NMR spectrum of compound 2h
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
6.00
3.02
0.92
1.03
2.03
1.12
1.00
1.00
0.97
1.59
77
2.24
65
6.98
556.
9888
7.00
397.
0071
7.02
227.
0254
7.05
897.
0800
7.09
287.
1095
7.11
197.
1495
7.16
827.
1914
7.21
067.
2975
7.31
637.
4559
7.45
807.
4745
7.47
657.
4931
7.49
537.
5310
7.53
377.
5497
7.55
237.
5682
7.57
087.
9383
7.95
72
13C NMR spectrum of compound 2h
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
18.1
7
27.9
5
87.8
9
120.
3312
1.68
123.
4212
4.06
125.
9912
8.64
129.
7913
0.11
131.
92
146.
2015
1.80
157.
01
S45
1H NMR spectrum of compound 2i
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
6.08
1.02
1.00
0.99
2.00
1.01
1.00
1.64
80
7.16
407.
1699
7.18
547.
1914
7.31
167.
3306
7.36
277.
3841
7.45
597.
4618
7.47
437.
4763
7.49
307.
4953
7.54
807.
5507
7.56
687.
5693
7.58
547.
5880
7.87
917.
8982
13C NMR spectrum of compound 2i
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
27.7
7
89.1
3
120.
3612
3.60
124.
1212
5.66
127.
0112
8.85
129.
6613
0.12
132.
0313
2.42
146.
52
151.
64
158.
97
S46
1H NMR spectrum of compound 2j
-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)
6.04
0.98
2.13
3.05
1.00
3.02
1.00
1.69
38
7.35
517.
3738
7.39
567.
3984
7.41
507.
4327
7.43
567.
4512
7.45
407.
4720
7.48
857.
4915
7.51
417.
5308
7.53
277.
5504
7.55
537.
5723
7.57
737.
5830
7.58
567.
6018
7.60
427.
6203
7.62
267.
7701
7.77
437.
8286
7.83
997.
8507
7.86
158.
0136
8.03
25
13C NMR spectrum of compound 2j
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
27.8
6
88.4
5
120.
2812
0.32
124.
1012
4.19
124.
5412
5.85
127.
6112
8.12
128.
7413
0.18
130.
8413
2.05
134.
1414
4.53
151.
62
158.
27
S47
1H NMR spectrum of compound 2k
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
6.04
2.96
1.12
1.00
1.01
1.00
1.66
90
3.95
95
7.23
717.
2560
7.27
027.
3622
7.36
447.
3810
7.38
317.
3997
7.40
217.
4405
7.44
317.
4593
7.46
187.
4779
7.48
047.
6432
7.66
23
13C NMR spectrum of compound 2k
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
27.9
8
62.7
0
90.3
7
120.
4312
1.79
127.
4412
8.58
130.
89
149.
48
155.
36
S48
1H NMR spectrum of compound 2l
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
1.07
9.17
1.00
1.01
2.05
2.92
1.00
0.97
1.37
551.
3906
1.39
601.
4087
1.41
631.
4409
1.73
801.
7459
1.75
591.
7628
1.79
061.
8249
1.83
21
7.08
697.
0897
7.09
267.
1081
7.12
347.
1263
7.12
927.
2940
7.31
267.
3290
7.33
367.
3379
7.35
437.
3679
7.37
297.
4382
7.44
327.
4459
7.45
667.
4591
7.46
417.
4672
7.47
517.
4778
7.50
087.
5039
7.51
957.
5223
7.53
807.
5407
7.93
667.
9554
13C NMR spectrum of compound 2l
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
22.6
024
.92
36.7
1
89.6
2
120.
5512
3.90
124.
1412
4.28
128.
5312
8.70
130.
6813
1.68
146.
6615
1.36
157.
91
S49
1H NMR spectrum of compound 2m
-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
8.09
1.00
4.94
1.00
1.00
0.97
1.88
001.
9047
1.91
831.
9252
1.93
321.
9470
1.95
031.
9591
1.97
201.
9907
1.99
502.
0037
2.01
452.
0314
2.05
972.
0751
2.08
092.
0939
2.10
002.
1126
2.13
192.
1431
7.07
627.
0804
7.08
437.
0939
7.09
767.
1012
7.11
017.
1148
7.11
887.
1451
7.31
247.
3151
7.33
187.
3369
7.35
467.
3598
7.36
347.
3757
7.38
077.
3850
7.44
307.
4449
7.46
177.
4635
7.48
037.
4823
7.52
887.
5313
7.54
757.
5499
7.56
607.
5684
7.91
877.
9377
13C NMR spectrum of compound 2m
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
25.0
7
40.1
2
98.2
5
120.
4512
3.73
123.
8512
3.97
128.
5512
8.60
131.
1213
1.97
146.
6914
9.36
157.
90
1H NMR spectrum of compound 2n
S50
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
9.00
1.98
2.20
2.00
1.98
1.02
5.00
2.01
0.97
1.49
661.
6544
1.71
331.
7471
1.97
342.
0155
2.03
822.
0465
2.06
98
3.17
75
4.18
66
7.10
337.
1066
7.12
117.
1242
7.13
867.
1420
7.16
287.
1815
7.26
307.
2669
7.28
447.
3030
7.33
657.
3538
7.37
147.
3746
7.39
307.
4103
7.41
347.
4829
7.50
167.
5203
7.54
147.
5599
7.57
837.
9571
7.97
59
13C NMR spectrum of compound 2n
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
28.4
8
36.0
7
79.9
2
87.1
3
120.
5312
4.05
124.
2012
4.33
128.
6412
9.23
130.
6113
2.06
146.
2714
9.60
154.
7715
6.92
1H NMR spectrum of compound 2o
S51
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
6.03
1.02
1.03
4.10
1.01
0.95
1.62
55
7.08
047.
0863
7.09
387.
1004
7.10
847.
1152
7.12
197.
1297
7.13
657.
1438
7.14
927.
1725
7.19
267.
3204
7.33
487.
3420
7.34
927.
3650
7.37
087.
6337
7.63
817.
6539
7.65
828.
0726
8.07
66
13C NMR spectrum of compound 2o
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
27.7
7
88.3
2
121.
9112
2.61
123.
7812
4.24
127.
1112
8.65
132.
5813
4.89
146.
2615
0.19
156.
14
1H NMR spectrum of compound 2p
S52
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
1.04
9.03
1.01
2.12
2.02
1.96
1.00
1.33
811.
3625
1.37
831.
3924
1.41
061.
4259
1.75
441.
7777
1.82
51
7.10
397.
1221
7.14
047.
1850
7.19
067.
2060
7.21
157.
2273
7.23
637.
2486
7.25
687.
2690
7.33
777.
3580
7.37
677.
4435
7.46
217.
5850
7.59
027.
6050
7.61
00
13C NMR spectrum of compound 2p
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
22.6
024
.83
36.8
3
89.6
2
110.
4311
0.67
119.
1911
9.43
122.
0112
2.09
124.
2512
4.35
128.
6013
3.04
146.
1814
6.92
156.
6416
1.93
164.
38
1H NMR spectrum of compound 2q
S53
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
1.05
9.15
2.05
2.06
2.00
1.00
0.94
1.33
631.
3611
1.37
701.
3925
1.40
801.
4245
1.75
351.
7763
1.80
671.
8191
1.82
75
7.10
347.
1063
7.10
907.
1246
7.14
007.
1429
7.14
567.
1668
7.18
707.
3379
7.34
207.
3586
7.37
217.
3772
7.43
967.
4422
7.45
607.
4604
7.46
357.
6092
7.61
367.
6293
7.63
378.
0848
8.08
88
13C NMR spectrum of compound 2q
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
22.5
124
.81
36.6
1
89.7
5
122.
1512
2.59
124.
3212
4.39
127.
1612
8.61
132.
9813
4.63
146.
0914
9.98
156.
20
1H NMR spectrum of compound 2r
S54
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
1.18
9.09
3.02
1.00
1.11
3.05
1.99
1.00
1.21
571.
2582
1.27
761.
2868
1.29
901.
3186
1.63
451.
6427
1.66
401.
6949
1.70
101.
7335
2.33
14
6.97
116.
9738
6.97
666.
9921
7.00
767.
0104
7.01
327.
0709
7.09
027.
2101
7.21
187.
2194
7.22
397.
2331
7.24
007.
2538
7.25
877.
3332
7.33
577.
3540
7.35
707.
6477
13C NMR spectrum of compound 2r
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
21.2
322
.66
24.9
4
36.7
9
89.5
6
120.
3012
3.83
124.
1912
4.31
128.
5113
0.85
132.
7513
8.75
146.
7214
8.83
158.
08
S55
1H NMR spectrum of compound 2s
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
1.10
9.24
1.00
1.12
2.03
2.91
1.00
1.33
961.
3686
1.38
431.
3984
1.41
531.
7238
1.72
711.
7824
1.83
18
7.11
067.
1283
7.14
557.
2258
7.22
837.
2460
7.24
827.
2570
7.26
137.
3407
7.34
367.
3608
7.37
887.
3823
7.44
567.
4677
7.48
407.
4884
7.52
397.
9213
13C NMR spectrum of compound 2s
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
22.5
324
.82
36.6
7
89.6
9
121.
8212
4.12
124.
2912
4.39
128.
6113
1.85
132.
7213
4.81
146.
1214
9.49
156.
32
S56
1H NMR spectrum of compound 2t
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
1.05
9.07
1.01
1.01
2.08
3.00
1.00
1.33
721.
3591
1.37
401.
3912
1.40
871.
7550
1.76
231.
7797
1.82
65
7.09
647.
0993
7.10
227.
1176
7.13
297.
1359
7.13
877.
2865
7.29
027.
3332
7.33
747.
3540
7.36
747.
3725
7.41
597.
4202
7.43
007.
4327
7.43
597.
4406
7.44
617.
4510
7.45
407.
8548
7.87
53
13C NMR spectrum of compound 2t
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
22.4
824
.81
36.6
1
89.2
4
121.
1112
4.19
124.
3012
5.42
128.
6012
9.33
137.
84
146.
2315
2.83
156.
68
S57
1H NMR spectrum of compound 2u
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
3.08
1.03
1.00
4.96
1.03
1.00
1.00
1.63
531.
6518
5.65
385.
6702
5.68
665.
7030
7.14
127.
3265
7.34
387.
3477
7.36
667.
3770
7.37
907.
3843
7.39
577.
3973
7.52
777.
5980
7.98
768.
0065
13C NMR spectrum of compound 2u
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
21.0
1
80.8
0
121.
0112
3.37
123.
9212
4.00
128.
6612
8.79
130.
6413
1.93
146.
7714
7.89
158.
56
S58
1H NMR spectrum of compound 3
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
6.06
1.00
1.02
1.01
1.00
1.67
32
7.43
377.
4381
7.45
287.
4573
7.50
177.
5059
7.52
057.
5246
7.53
917.
5434
7.66
987.
6733
7.68
867.
6920
7.70
717.
7109
7.71
347.
8580
7.85
957.
8770
13C NMR spectrum of compound 3
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
27.3
3
85.4
6
120.
7412
5.22
125.
6712
8.94
134.
19
154.
97
169.
84
S59
4. X-ray single crystal data for product
2b
O
NBr
Table 1. Crystal data and structure refinement for 2b.
Identification code 2b
Empirical formula C16 H14 Br N O
Formula weight 316.19
Temperature 113(2) K
Wavelength 0.71073 A
Crystal system, space group Monoclinic, P2(1)/n
Unit cell dimensions a = 15.304(3) A alpha = 90 deg.
b = 5.8888(12) A beta = 106.59(3) deg.
c = 16.007(3) A gamma = 90 deg.
Volume 1382.6(5) A^3
Z, Calculated density 4, 1.519 Mg/m^3
Absorption coefficient 2.964 mm^-1
F(000) 640
Crystal size 0.200 x 0.180 x 0.120 mm
Theta range for data collection 1.624 to 27.899 deg.
S60
Limiting indices -19<=h<=20, -7<=k<=7, -21<=l<=21
Reflections collected / unique 14182 / 3309 [R(int) = 0.0632]
Completeness to theta = 25.242 100.0 %
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 1 and 0.5159
Refinement method Full-matrix least-squares on F^2
Data / restraints / parameters 3309 / 0 / 175
Goodness-of-fit on F^2 0.983
Final R indices [I>2sigma(I)] R1 = 0.0434, wR2 = 0.0906
R indices (all data) R1 = 0.0598, wR2 = 0.0978
Extinction coefficient 0.0337(15)
Largest diff. peak and hole 0.745 and -0.584 e.A^-3
Table 2. Atomic coordinates ( x 10^4) and equivalent isotropic
displacement parameters (A^2 x 10^3) for shelxl.
U(eq) is defined as one third of the trace of the orthogonalized
Uij tensor.
________________________________________________________________
x y z U(eq)
________________________________________________________________
Br(1) 9110(1) 786(1) 8366(1) 34(1)
O(1) 7342(1) 8403(3) 5116(1) 25(1)
N(1) 8868(2) 7289(4) 5356(1) 23(1)
C(1) 8181(2) 8513(4) 4980(2) 21(1)
C(2) 8157(2) 10292(4) 4340(2) 21(1)
C(3) 8844(2) 11115(5) 4011(2) 29(1)
C(4) 8638(2) 12925(5) 3441(2) 35(1)
C(5) 7773(2) 13898(5) 3202(2) 33(1)
C(6) 7094(2) 13071(5) 3536(2) 29(1)
C(7) 7297(2) 11265(4) 4106(2) 22(1)
S61
C(8) 6720(2) 10080(5) 4594(2) 23(1)
C(9) 5912(2) 8828(5) 4010(2) 31(1)
C(10) 6448(2) 11674(5) 5227(2) 34(1)
C(11) 8842(2) 5758(4) 6027(2) 21(1)
C(12) 9350(2) 3764(5) 6096(2) 26(1)
C(13) 9410(2) 2255(5) 6771(2) 27(1)
C(14) 8981(2) 2765(5) 7397(2) 25(1)
C(15) 8480(2) 4730(5) 7352(2) 27(1)
C(16) 8409(2) 6212(5) 6667(2) 28(1)
________________________________________________________________
Table 3. Bond lengths [A] and angles [deg] for shelxl.
_____________________________________________________________
Br(1)-C(14) 1.904(3)
O(1)-C(1) 1.363(3)
O(1)-C(8) 1.458(3)
N(1)-C(1) 1.275(3)
N(1)-C(11) 1.412(3)
C(1)-C(2) 1.458(4)
C(2)-C(7) 1.385(4)
C(2)-C(3) 1.391(4)
C(3)-C(4) 1.380(4)
C(3)-H(3) 0.9500
C(4)-C(5) 1.391(4)
C(4)-H(4) 0.9500
C(5)-C(6) 1.386(4)
C(5)-H(5) 0.9500
C(6)-C(7) 1.378(4)
C(6)-H(6) 0.9500
C(7)-C(8) 1.507(4)
C(8)-C(9) 1.512(4)
S62
C(8)-C(10) 1.524(4)
C(9)-H(9A) 0.9800
C(9)-H(9B) 0.9800
C(9)-H(9C) 0.9800
C(10)-H(10A) 0.9800
C(10)-H(10B) 0.9800
C(10)-H(10C) 0.9800
C(11)-C(12) 1.395(4)
C(11)-C(16) 1.395(4)
C(12)-C(13) 1.382(4)
C(12)-H(12) 0.9500
C(13)-C(14) 1.378(4)
C(13)-H(13) 0.9500
C(14)-C(15) 1.379(4)
C(15)-C(16) 1.382(4)
C(15)-H(15) 0.9500
C(16)-H(16) 0.9500
C(1)-O(1)-C(8) 111.57(19)
C(1)-N(1)-C(11) 121.5(2)
N(1)-C(1)-O(1) 125.7(2)
N(1)-C(1)-C(2) 126.2(2)
O(1)-C(1)-C(2) 108.0(2)
C(7)-C(2)-C(3) 121.1(3)
C(7)-C(2)-C(1) 108.6(2)
C(3)-C(2)-C(1) 130.2(2)
C(4)-C(3)-C(2) 117.7(3)
C(4)-C(3)-H(3) 121.2
C(2)-C(3)-H(3) 121.2
C(3)-C(4)-C(5) 121.3(3)
S63
C(3)-C(4)-H(4) 119.3
C(5)-C(4)-H(4) 119.3
C(6)-C(5)-C(4) 120.5(3)
C(6)-C(5)-H(5) 119.7
C(4)-C(5)-H(5) 119.7
C(7)-C(6)-C(5) 118.4(3)
C(7)-C(6)-H(6) 120.8
C(5)-C(6)-H(6) 120.8
C(6)-C(7)-C(2) 121.0(3)
C(6)-C(7)-C(8) 130.3(3)
C(2)-C(7)-C(8) 108.7(2)
O(1)-C(8)-C(7) 103.1(2)
O(1)-C(8)-C(9) 108.0(2)
C(7)-C(8)-C(9) 113.7(2)
O(1)-C(8)-C(10) 107.1(2)
C(7)-C(8)-C(10) 111.8(2)
C(9)-C(8)-C(10) 112.5(2)
C(8)-C(9)-H(9A) 109.5
C(8)-C(9)-H(9B) 109.5
H(9A)-C(9)-H(9B) 109.5
C(8)-C(9)-H(9C) 109.5
H(9A)-C(9)-H(9C) 109.5
H(9B)-C(9)-H(9C) 109.5
C(8)-C(10)-H(10A) 109.5
C(8)-C(10)-H(10B) 109.5
H(10A)-C(10)-H(10B) 109.5
C(8)-C(10)-H(10C) 109.5
H(10A)-C(10)-H(10C) 109.5
H(10B)-C(10)-H(10C) 109.5
C(12)-C(11)-C(16) 118.3(2)
S64
C(12)-C(11)-N(1) 117.5(2)
C(16)-C(11)-N(1) 124.0(2)
C(13)-C(12)-C(11) 121.0(3)
C(13)-C(12)-H(12) 119.5
C(11)-C(12)-H(12) 119.5
C(14)-C(13)-C(12) 119.3(3)
C(14)-C(13)-H(13) 120.4
C(12)-C(13)-H(13) 120.4
C(13)-C(14)-C(15) 121.2(3)
C(13)-C(14)-Br(1) 119.9(2)
C(15)-C(14)-Br(1) 118.9(2)
C(14)-C(15)-C(16) 119.2(3)
C(14)-C(15)-H(15) 120.4
C(16)-C(15)-H(15) 120.4
C(15)-C(16)-C(11) 121.1(3)
C(15)-C(16)-H(16) 119.5
C(11)-C(16)-H(16) 119.5
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:
Table 4. Anisotropic displacement parameters (A^2 x 10^3) for shelxl.
The anisotropic displacement factor exponent takes the form:
-2 pi^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ]
_______________________________________________________________________
U11 U22 U33 U23 U13 U12
_______________________________________________________________________
Br(1) 37(1) 33(1) 32(1) 8(1) 9(1) 0(1)
O(1) 13(1) 36(1) 26(1) 10(1) 6(1) 4(1)
N(1) 20(1) 28(1) 22(1) 1(1) 6(1) 2(1)
C(1) 18(1) 25(1) 19(1) -3(1) 5(1) 0(1)
C(2) 20(1) 26(1) 19(1) -3(1) 7(1) -2(1)
S65
C(3) 23(1) 41(2) 23(1) -3(1) 8(1) -4(1)
C(4) 38(2) 43(2) 24(2) 0(1) 10(1) -16(1)
C(5) 50(2) 24(2) 25(2) 4(1) 10(1) -3(1)
C(6) 34(2) 24(2) 28(2) -1(1) 7(1) 6(1)
C(7) 26(1) 22(1) 17(1) -4(1) 6(1) 0(1)
C(8) 18(1) 26(1) 25(1) 3(1) 7(1) 6(1)
C(9) 20(1) 34(2) 38(2) 1(1) 6(1) 1(1)
C(10) 35(2) 42(2) 29(2) -2(1) 16(1) 10(1)
C(11) 15(1) 26(1) 20(1) 0(1) 2(1) -1(1)
C(12) 23(1) 29(2) 28(1) -2(1) 10(1) -1(1)
C(13) 29(2) 24(1) 30(2) -2(1) 9(1) 4(1)
C(14) 23(1) 27(1) 22(1) 1(1) 3(1) -2(1)
C(15) 22(1) 38(2) 23(1) 0(1) 8(1) 4(1)
C(16) 27(2) 33(2) 26(1) 0(1) 9(1) 8(1)
_______________________________________________________________________
Table 5. Hydrogen coordinates ( x 10^4) and isotropic displacement parameters (A^2 x 10^3) for shelxl.
________________________________________________________________
x y z U(eq)
________________________________________________________________
H(3) 9435 10454 4173 34
H(4) 9095 13519 3206 42
H(5) 7648 15140 2807 40
H(6) 6503 13733 3375 34
H(9A) 6123 7781 3633 47
H(9B) 5485 9923 3650 47
H(9C) 5606 7969 4369 47
H(10A) 6147 10804 5588 51
H(10B) 6029 12832 4899 51
H(10C) 6994 12411 5602 51
H(12) 9659 3439 5673 31
S66
H(13) 9744 881 6804 33
H(15) 8186 5060 7787 33
H(16) 8061 7563 6631 34
________________________________________________________________
Table 6. Torsion angles [deg] for shelxl.
________________________________________________________________
C(11)-N(1)-C(1)-O(1) -5.1(4)
C(11)-N(1)-C(1)-C(2) 173.9(2)
C(8)-O(1)-C(1)-N(1) 178.6(2)
C(8)-O(1)-C(1)-C(2) -0.6(3)
N(1)-C(1)-C(2)-C(7) -178.3(2)
O(1)-C(1)-C(2)-C(7) 0.9(3)
N(1)-C(1)-C(2)-C(3) -2.0(5)
O(1)-C(1)-C(2)-C(3) 177.2(3)
C(7)-C(2)-C(3)-C(4) -0.3(4)
C(1)-C(2)-C(3)-C(4) -176.2(3)
C(2)-C(3)-C(4)-C(5) 0.0(4)
C(3)-C(4)-C(5)-C(6) 0.2(4)
C(4)-C(5)-C(6)-C(7) -0.1(4)
C(5)-C(6)-C(7)-C(2) -0.1(4)
C(5)-C(6)-C(7)-C(8) 177.3(3)
C(3)-C(2)-C(7)-C(6) 0.3(4)
C(1)-C(2)-C(7)-C(6) 177.1(2)
C(3)-C(2)-C(7)-C(8) -177.6(2)
C(1)-C(2)-C(7)-C(8) -0.8(3)
C(1)-O(1)-C(8)-C(7) 0.1(3)
C(1)-O(1)-C(8)-C(9) 120.7(2)
C(1)-O(1)-C(8)-C(10) -118.0(2)
C(6)-C(7)-C(8)-O(1) -177.2(3)
C(2)-C(7)-C(8)-O(1) 0.5(3)
S67
C(6)-C(7)-C(8)-C(9) 66.2(4)
C(2)-C(7)-C(8)-C(9) -116.2(2)
C(6)-C(7)-C(8)-C(10) -62.5(4)
C(2)-C(7)-C(8)-C(10) 115.2(2)
C(1)-N(1)-C(11)-C(12) 147.4(3)
C(1)-N(1)-C(11)-C(16) -38.6(4)
C(16)-C(11)-C(12)-C(13) 1.2(4)
N(1)-C(11)-C(12)-C(13) 175.5(2)
C(11)-C(12)-C(13)-C(14) -1.8(4)
C(12)-C(13)-C(14)-C(15) 1.2(4)
C(12)-C(13)-C(14)-Br(1) -176.7(2)
C(13)-C(14)-C(15)-C(16) -0.1(4)
Br(1)-C(14)-C(15)-C(16) 177.8(2)
C(14)-C(15)-C(16)-C(11) -0.5(4)
C(12)-C(11)-C(16)-C(15) 0.0(4)
N(1)-C(11)-C(16)-C(15) -174.0(3)
________________________________________________________________
Symmetry transformations used to generate equivalent atoms:
Table 7. Hydrogen bonds for shelxl [A and deg.].
____________________________________________________________________________
D-H...A d(D-H) d(H...A) d(D...A) <(DHA)
5. Analytical data of HRMS
When 2.0 eq TEMPO or BHT was added to the above reaction mixture, the reaction
was inhibited. When 2.0 eq TEMPO or BHT was added to the reaction of 1a, the
reaction was monitored by mass spectrometry experiment. Byproducts 4 and 5 were
observed by mass spectrometry, which corresponds to the products of the radical
captured by TEMPO and BHT. So we think this is a radical mechanism.
In addition, when we carried out the reaction in the solvent of DCE (Table 1, entry 1),
intermolecular oxidation product 6 was detected by mass spectrometry, suggesting
S68
that an alkyl cation had been generated.
Calc. 395.2693Found: 395.2689
O
NHPh
ON
[M + H]+
4
S69
Calc. 458.3054Found: 458.3053
O
NHPh
O
5
S70
Calc. 508.0380Found: 508.0375
O
NHPh
O
O
I
6