thieme · supporting information copper-catalyzed direct c-5 fluorination of 8-aminoquinolines by...
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Thieme
Supporting Information for DOI: 10.1055/s-0037-1610130
© Georg Thieme Verlag KG Stuttgart · New York 2018
Supporting Information Copper-catalyzed direct C-5 fluorination of 8-aminoquinolines by remote C-H
activation Si-Si Luoa, Lan-Jun Sua, Yue Jianga, Xiao-Bao Lib, Zheng-Hui Lia, Huan Suna* and Ji-Kai Liua*
a: School of Pharmaceutical Sciences, South-Central University for Nationalities, Wuhan, 430074, P. R.
China
*Email: [email protected]
*Email: [email protected]
b: Department of Civil and Environmental Engineering, Northwestern University. Evanston, IL, USA.
60060.
Table of Contents: General inforamtion 2
Characterization data of products 3
References 7
NMR Spectra Images of Products 8
2
General information:
All reactions were carried out under an N2 atmosphere (balloon) with dry solvents under anhydrous
conditions. All reagents were purchased from Adamas and used without further purification unless
specified otherwise. Solvents for chromatography were technical grade and distilled prior to use. Flash
chromatography was performed using 200-300 mesh silica gel with the indicated solvent system
according to standard techniques. Analytical thin-layer chromatography (TLC) was performed on
pre-coated, glass-backed silica gel plates. Visualization of the developed chromatogram was performed
by UV absorbance (254 nm). 1H NMR and 13C NMR data were recorded on Bruker 600 M nuclear
resonance spectrometers unless otherwise specified, respectively. Chemical shifts (δ) in ppm are
reported as quoted relative to the residual signals of chloroform (1H 7.26 ppm or 13C 77.16 ppm).
Multiplicities are described as: s (singlet), bs (broad singlet), d (doublet), t (triplet), q (quartet), m
(multiplet); and coupling constants (J) are reported in Hertz (Hz). 13C NMR spectra were recorded
with total proton decoupling. HRMS (ESI) analysis was performed by The Analytical Instrumentation
Center at School of Pharmaceutical Sciences, South-Central University for Nationalities, and (HRMS)
data were reported with ion mass/charge (m/z) ratios as values in atomic mass units.
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Characterization data of products
8-aminoquinoline deravitives 11 (0.1 mmol, 1.0 eq.), Cu(OAc)2 (0.02 mmol, 0.2 eq.), Selectfluoro (0.15 mmol, 1.5
eq.), KH2PO4 (0.2 mmol, 2.0 eq.), and Na2SO4 (50 mg) were weighed into an oven dried Schlenk tube, and MeOH
(1mL) was added. The reaction vessel was capped and vacuum-flushed with N2 three times. The reaction was
stirred under N2 atmosphere at 80 °C and the progress of the fluorination was monitored by TLC. Upon complete
consumption of 1, the reaction was cooled to room temperature. Volatile solvent and reagents were removed by
rotary evaportion and the residue was purified by selica gel flsh chromatography using petroleum ether/EtOAc
(100:1 to 20:1) to afford fluorinated product 22.
N-(5-fluoroquinolin-8-yl)-4-methylbenzamide (2a): 45% yield, white solid. 1H NMR (600 MHz, Chloroform-d) δ
10.52 (s, 1H), 8.94-8.85 (m, 2H), 8.47 (dd, J = 8.4, 1.7 Hz, 1H), 8.01-7.94 (m, 2H), 7.56 (dd, J = 8.4, 4.2 Hz, 1H),
7.40-7.33 (m, 2H), 7.30-7.27 (m, 1H), 2.46 (s, 3H). 13C NMR (151 MHz, Chloroform-d) δ 165.48, 153.87 (d,
J=250.7 Hz), 149.22, 142.55, 139.09 (d, J=3.0 Hz), 132.28, 131.35 (d, J=3.0 Hz), 129.98 (d, J=3.0 Hz), 129.62,
127.37, 121.87 (d, J=3.0 Hz), 119.00 (d, J=3.0 Hz), 116.09 (d, J=7.6 Hz), 110.72 (d, J=19.6 Hz), 21.71. 19F NMR
(565 MHz, CDCl3) δ -129.22. HRMS (ESI): m/z = 281.1086, calcd. for C17H14ON2F ([M+H]+) 281.1090.
N-(7-fluoroquinolin-8-yl)-4-methylbenzamide: white solid. 1H NMR (600 MHz, Chloroform-d) δ 9.15 (s, 1H), 8.84
(dd, J = 4.2, 1.7 Hz, 1H), 8.19 (dd, J = 8.3, 1.7 Hz, 1H), 8.02 (d, J = 8.3 Hz, 2H), 7.69 (dd, J = 9.1, 5.2 Hz, 1H),
7.50 (t, J = 9.5 Hz, 1H), 7.44 (dd, J = 8.3, 4.2 Hz, 1H), 7.34 (d, J = 7.9 Hz, 2H), 2.46 (s, 3H). 13C NMR (151 MHz,
Chloroform-d) δ 165.42, 153.50 (d, J=255.2 Hz), 150.02, 142.81, 142.76, 136.37, 131.42, 129.50, 128.13, 125.24
(d, J=7.6 Hz), 125.13, 121.00 (d, J=1.5 Hz), 120.34 (d, J=12.1 Hz), 118.64 (d, J=24.2 Hz), 21.75. 19F NMR (565
MHz, CDCl3) δ. -108.41 HRMS (ESI): m/z =281.1084, calcd. for C17H14ON2F ([M+H]+) 281.1090.
N-(5,7-difluoroquinolin-8-yl)-4-methylbenzamide: white solid. 1H NMR (600 MHz, Chloroform-d) δ 8.90 (dd, J =
4.3, 1.7 Hz, 1H), 8.86 (s, 1H), 8.43 (dd, J = 8.4, 1.7 Hz, 1H), 7.98 (d, J= 8.2 Hz, 2H), 7.50 (dd, J = 8.4, 4.2 Hz,
1H), 7.34 (d, J = 7.9 Hz, 2H), 7.23 (t, J = 9.8 Hz, 1H), 2.46 (s, 3H). 19F NMR (565 MHz, CDCl3) δ. -106.45,
-123.32. HRMS (ESI): m/z =299.0990, calcd. for C17H13ON2F2 ([M+H]+) 299.0996.
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N-(5-fluoroquinolin-8-yl)benzamide (2b): 42% yield, white solid. 1H NMR (600 MHz, Chloroform-d) δ 10.55 (s,
1H), 8.95-8.87 (m, 2H), 8.48 (dt, J = 8.4, 1.7 Hz, 1H), 8.10-8.05 (m, 2H), 7.63-7.54 (m, 4H), 7.31-7.27 (m, 1H). 13C NMR (151 MHz, Chloroform-d) δ 165.38, 153.86 (d, J=250.7 Hz), 149.16, 138.99 (d, J=1.5 Hz), 135.00,
131.92, 131.14 (d, J=4.5 Hz), 129.91 (d, J=3.0 Hz), 128.85, 127.26, 121.80 (d, J=3.0 Hz), 118.91 (d, J=18.1 Hz),
116.09 (d, J=7.6 Hz), 110.62 (d, J=19.6 Hz). 19F NMR (565 MHz, CDCl3) δ -128.95. HRMS (ESI): m/z =267.0927,
calcd. for C16H12ON2F ([M+H]+) 267.0934.
N-(5-fluoroquinolin-8-yl)-4-methoxybenzamide (2c): 28% yield, white solid. 1H NMR (600 MHz, Chloroform-d) δ
10.48 (s, 1H), 8.93-8.83 (m, 2H), 8.47 (dd, J = 8.4, 1.6 Hz, 1H), 8.08-7.99 (m, 2H), 7.56 (dd, J = 8.4, 4.3 Hz, 1H),
7.30-7.24 (m, 1H), 7.10-6.98 (m, 2H), 3.91 (s, 3H). 13C NMR (151 MHz, Chloroform-d) δ 164.92, 162.53, 153.68
(d, J=250.7 Hz), 149.07, 138.96 (d, J=3.0 Hz), 131.32 (d, J=4.5 Hz), 129.88 (d, J=3.0 Hz), 129.14, 127.27, 121.74
(d, J=3.0 Hz), 118.89 (d, J=3.0 Hz), 115.86 (d, J=7.6 Hz), 114.01, 110.63 (d, J=19.6 Hz), 55.51. 19F NMR (565
MHz, CDCl3) δ -129.42. HRMS (ESI): m/z = 297.1034, calcd. for C17H14O2N2F ([M+H]+) 297.1039.
4-chloro-N-(5-fluoroquinolin-8-yl)benzamide (2d): 35% yield, white solid. 1H NMR (600 MHz, Chloroform-d) δ
10.51 (s, 1H), 8.91 (dt, J = 4.1, 1.9 Hz, 1H), 8.89-8.84 (m, 1H), 8.47 (dq, J = 8.4, 1.7 Hz, 1H), 8.01 (dt, J = 8.5, 1.7
Hz, 2H), 7.57 (dt, J = 6.1, 2.9 Hz, 1H), 7.55-7.50 (m, 2H), 7.30-7.24 (m, 1H). 13C NMR (151 MHz, Chloroform-d)
δ 164.22, 153.97 (d, J=252.2 Hz), 149.22, 138.93 (d, J=3.0 Hz), 138.20, 133.35, 130.88 (d, J=4.5 Hz), 129.97 (d,
J=3.0 Hz), 129.11, 128.68, 121.87 (d, J=3.0 Hz), 118.91 (d, J=18.1 Hz), 116.16 (d, J=7.6 Hz), 110.60 (d, J=19.6
Hz). 19F NMR (565 MHz, CDCl3) δ -128.55. HRMS (ESI): m/z = 301.0539, calcd. for C16H11ON2FCl ([M+H]+)
301.0544.
N-(5-fluoroquinolin-8-yl)-3-methylbenzamide (2e): 32% yield, white solid. 1H NMR (600 MHz, Chloroform-d) δ
10.50 (s, 1H), 8.94-8.86 (m, 2H), 8.46 (dd, J = 8.4, 1.7 Hz, 1H), 7.87 (s, 1H), 7.86 (d, J=7.8 Hz, 1H), 7.55 (dd, J =
8.4, 4.2 Hz, 1H), 7.47-7.37 (m, 2H), 7.26 (d, J = 5.3 Hz, 1H), 2.49 (s, 3H). 13C NMR (151 MHz, Chloroform-d) δ
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165.61, 153.82 (d, J=252.2 Hz), 149.14, 138.99 (d, J=3.0 Hz), 138.73, 135.00, 132.68, 131.20 (d, J=4.5 Hz),
129.88(d, J=4.5 Hz), 128.69, 128.03, 124.17, 121.77(d, J=3.0 Hz), 118.89 (d, J=18.1 Hz), 116.07 (d, J=7.6 Hz),
110.60 (d, J=19.6 Hz), 21.53. 19F NMR (565 MHz, CDCl3) δ -129.06. HRMS (ESI): m/z = 281.1084, calcd. for
C17H14ON2F ([M+H]+) 281.1090.
3-chloro-N-(5-fluoroquinolin-8-yl)benzamide (2f): 30% yield, white solid. 1H NMR (600 MHz, Chloroform-d) δ
10.50 (s, 1H), 8.93 (dd, J = 4.2, 1.6 Hz, 1H), 8.87 (dd, J = 8.6, 5.3 Hz, 1H), 8.48 (dd, J = 8.4, 1.6 Hz, 1H), 8.05 (t, J
= 1.9 Hz, 1H), 7.94 (d, J = 7.7, 1H), 7.62-7.54 (m, 2H), 7.50 (t, J = 7.8 Hz, 1H), 7.31-7.27 (m, 1H). 13C NMR (151
MHz, Chloroform-d) δ 163.93, 154.05 (d, J=252.2 Hz), 149.28, 138.95(d, J=3.0 Hz), 136.78, 135.06, 131.96,
130.80 (d, J=4.5Hz), 130.15, 129.98 (d, J=3.0 Hz), 127.67, 125.25, 121.90 (d, J=3.0 Hz), 118.92 (d, J=3.0 Hz),
116.29 (d, J=7.6 Hz), 110.59 (d, J=19.6 Hz). 19F NMR (565 MHz, CDCl3) δ -128.38. HRMS (ESI): m/z =
301.0539, calcd. for C16H11ON2FCl ([M+H]+) 301.0544.
4-fluoro-N-(5-fluoroquinolin-8-yl)benzamide (2g): 38% yield, white solid. 1H NMR (600 MHz, Chloroform-d) δ
10.50 (s, 1H), 8.91 (dd, J = 4.2, 1.6 Hz, 1H), 8.87 (dd, J = 8.6, 5.3 Hz, 1H), 8.48 (dd, J = 8.4, 1.7 Hz, 1H), 8.12
-8.06 (m, 2H), 7.57 (dd, J = 8.4, 4.2 Hz, 1H), 7.30-7.23 (m, 3H). 13C NMR (151 MHz, Chloroform-d) δ 165.83,
164.23, 164.16, 153.89 (d, J=252.2 Hz), 149.16, 138.92 (d, J=3.0 Hz), 131.16 (d, J=3.0 Hz), 130.96 (d, J=4.5 Hz),
129.95 (d, J=4.5 Hz), 129.64 (d, J=9.1 Hz), 121.82 (d, J=1.5 Hz), 118.90 (d, J=18.1 Hz), 116.07 (d, J=9.1 Hz),
115.97 (d, J=22.6 Hz), 110.59 (d, J=19.6 Hz). 19F NMR (565 MHz, CDCl3) δ -107.51, -128.74. HRMS (ESI): m/z
= 285.0833, calcd. for C16H11ON2F2 ([M+H]+) 285.0839.
4-bromo-N-(5-fluoroquinolin-8-yl)benzamide (2h): 31% yield, white solid. 1H NMR (600 MHz, Chloroform-d) δ
10.51 (s, 1H), 8.91 (dd, J = 4.3, 1.7 Hz, 1H), 8.87 (dd, J = 8.6, 5.3 Hz, 1H), 8.48 (dd, J = 8.4, 1.7 Hz, 1H), 7.96 (d,
J=8.4 Hz, 2H), 7.72 (d, J=8.4 Hz, 2H), 7.57 (dd, J = 8.4, 4.2 Hz, 1H), 7.30-7.27 (m, 1H). 13C NMR (151 MHz,
Chloroform-d) δ 164.34, 153.99 (d, J=252.2 Hz), 149.23, 138.93 (d, J=3.0 Hz), 133.82, 132.09, 130.86 (d, J=4.5
Hz), 129.98 (d, J=3.0 Hz), 128.85, 126.70, 121.88 (d, J=3.0 Hz), 118.92 (d, J=18.1 Hz), 116.19 (d, J=9.1 Hz),
110.61 (d, J=19.6 Hz). 19F NMR (565 MHz, CDCl3) δ -128.51. HRMS (ESI): m/z = 345.0034, calcd. for
C16H11ON2FBr ([M+H]+) 345.0039.
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N-(5-fluoroquinolin-8-yl)-2,6-dimethoxybenzamide (2i): 34% yield, white solid. 1H NMR (600 MHz,
Chloroform-d) δ 10.10 (s, 1H), 8.99 (dd, J = 7.6, 1.3 Hz, 1H), 8.78 (dd, J = 4.2, 1.7 Hz, 1H), 8.18 (dd, J = 8.2, 1.7
Hz, 1H), 7.61 (t, J = 7.9 Hz, 1H), 7.56 (dd, J = 8.3, 1.4 Hz, 1H), 7.45 (dd, J = 8.2, 4.2 Hz, 1H), 7.14 (dd, J = 11.2,
9.1 Hz, 1H), 6.64 (dd, J = 9.2, 3.3 Hz, 1H), 4.01 (d, J = 1.9 Hz, 3H), 3.83 (s, 3H). 13C NMR (151 MHz,
Chloroform-d) δ 162.92 (d, J=3.0 Hz), 153.18 (d, J=3.0 Hz), 150.80 (d, J=241.6 Hz), 148.35, 145.77 (d, J=12.1 Hz)
138.60, 136.44, 134.76, 128.10, 127.60, 121.97, 121.73, 117.79 (d, J=21.1 Hz), 117.01, 106.10 (d, J=7.6 Hz),
62.32 (d, J=4.5 Hz), 56.49. 19F NMR (565 MHz, CDCl3) δ -139.30, -139.33. HRMS (ESI): m/z = 327.1140, calcd.
for C18H16O3N2F ([M+H]+) 327.1145.
2,3,4,5,6-pentafluoro-N-(5-fluoroquinolin-8-yl)benzamide (2j): 23% yield, white solid. 1H NMR (600 MHz,
Chloroform-d) δ 10.19 (s, 1H), 8.87 (ddd, J = 4.7, 3.0, 1.7 Hz, 1H), 8.83 (ddd, J = 8.9, 5.3, 3.8 Hz, 1H), 8.48 (ddd,
J = 8.4, 4.2, 1.7 Hz, 1H), 7.58 (ddd, J = 8.5, 4.2, 2.9 Hz, 1H), 7.32-7.27 (m, 1H). 13C NMR (151 MHz,
Chloroform-d) δ 155.23, 154.61 (d, J=253.7 Hz), 149.49, 145.35 (m), 143.66 (m), 141.81 (m), 138.65 (m), 136.98
(m), 130.07 (m), 122.08, 118.90 (dd, J=18.4, 3.6 Hz), 116.99 (d, J=9.1 Hz), 116.94 (m), 110.51(dd, J=19.6, 2.8 Hz). 19F NMR (565 MHz, Chloroform-d) δ -126.79 , -139.92 (d, J = 19.0 Hz), -149.94 (d, J = 20.9 Hz), -149.99 ,
-159.64 (t, J = 19.2 Hz). HRMS (ESI): m/z = 357.0457, calcd. for C16H7ON2F6 ([M+H]+) 357.0463.
N-(5-fluoroquinolin-8-yl)thiophene-3-carboxamide (2m): 25% yield, yellow solid. 1H NMR (600 MHz,
Chloroform-d) δ 10.35 (s, 1H), 8.91 (dd, J = 4.2, 1.7 Hz, 1H), 8.85 (dd, J = 8.6, 5.4 Hz, 1H), 8.47 (dd, J = 8.4, 1.2
Hz, 1H), 8.16 (dd, J = 3.0, 1.3 Hz, 1H), 7.69 (dd, J = 5.1, 1.3 Hz, 1H), 7.57 (dd, J = 8.4, 4.2 Hz, 1H), 7.45 (dd, J =
5.0, 3.0 Hz, 1H), 7.29 (m, 1H). 13C NMR (151 MHz, Chloroform-d) δ 161.07, 153.93 (d, J=250.7 Hz), 149.27,
138.93 (d, J=3.0 Hz), 138.28, 131.15 (d, J=4.5 Hz), 130.05 (d, J=4.5 Hz), 129.11, 126.95, 126.41, 121.93 (d, J=3.0
Hz), 119.02 (d, J=16.6 Hz), 116.15 (d, J=7.6Hz), 110.76 (d, J=19.6 Hz). 19F NMR (565 MHz, CDCl3) δ -129.07.
HRMS (ESI): m/z = 273.0491, calcd. for C14H10FN2OS ([M+H]+) 273.0498.
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2-chloro-N-(5-fluoroquinolin-8-yl)benzamide (2n): 41% yield, white solid. 1H NMR (600 MHz, Chloroform-d) δ
10.33 (s, 1H), 8.92 (dd, J = 8.6, 5.4 Hz, 1H), 8.86 (dd, J = 4.2, 1.7 Hz, 1H), 8.47 (dd, J = 8.4, 1.7 Hz, 1H), 7.82 (dd,
J = 7.5, 1.9 Hz, 1H), 7.55 (dd, J = 8.4, 4.2 Hz, 1H), 7.52 (dd, J = 7.8, 1.4 Hz, 1H), 7.44 (m, 2H), 7.32-7.27 (m, 1H). 13C NMR (151 MHz, Chloroform-d) δ 164.87, 154.22 (d, J=250.7 Hz), 149.38, 139.03 (d, J=3.0 Hz), 135.75,
131.74, 131.28, 131.10 (d, J=4.5 Hz), 131.07, 130.68, 130.26, 129.96 (d, J=3.0 Hz), 127.33, 121.94 (d, J=1.5 Hz),
119.00 (d, J=3.0 Hz), 116.62 (d, J=7.6 Hz), 110.67 (d, J=19.6 Hz). 19F NMR (565 MHz, CDCl3) δ -128.33. HRMS
(ESI): m/z = 301.0541, calcd. for C16H11FN2OCl ([M+H]+) 301.0544.
N-(5-fluoroquinolin-8-yl)-2-methylbenzamide (2o): 34% yield, white solid. 1H NMR (600 MHz, Chloroform-d) δ
10.02 (s, 1H), 8.91 (dd, J = 8.6, 5.4 Hz, 1H), 8.84 (dd, J = 4.2, 1.7 Hz, 1H), 8.47 (dd, J = 8.4, 1.7 Hz, 1H), 7.68 (dd,
J = 7.5, 1.4 Hz, 1H), 7.54 (dd, J = 8.4, 4.2 Hz, 1H), 7.42 (m, 1H), 7.36-7.31 (m, 2H), 7.31-7.27 (m, 1H), 2.61 (s,
3H). 13C NMR (151 MHz, Chloroform-d) δ 168.21, 154.02 (d, J=252.2 Hz), 149.25, 138.99 (d, J=4.5 Hz), 136.84,
136.60, 131.54, 131.41 (d, J=4.5 Hz), 130.53, 129.98 (d, J=3.0 Hz), 127.36, 126.17, 121.89 (d, J=3.0 Hz), 119.01
(d, J=3.0 Hz), 116.18 (d, J=7.6 Hz), 110.67 (d, J=19.6 Hz), 20.36. 19F NMR (565 MHz, CDCl3) δ -128.88. HRMS
(ESI): m/z = 281.1084, calcd. for C17H14ON2F ([M+H]+) 281.1090.
N-(5-fluoroquinolin-8-yl)pivalamide (2p): 36% yield, white solid. 1H NMR (600 MHz, Chloroform-d) δ 10.08 (s,
1H), 8.87 (dd, J = 4.3, 1.6 Hz, 1H), 8.76 (dd, J = 8.6, 5.4 Hz, 1H), 8.44 (dd, J = 8.4, 1.7 Hz, 1H), 7.53 (dd, J = 8.4,
4.2 Hz, 1H), 7.21 (t, J = 9.2 Hz, 1H), 1.43 (s, 9H). 13C NMR (151 MHz, Chloroform-d) δ 177.25, 153.67 (d,
J=250.7 Hz), 149.18, 139.09 (d, J=3.0 Hz), 131.36 (d, J=3.0 Hz), 129.90 (d, J=4.5 Hz), 121.74 (d, J=3.0 Hz),
118.91 (d, J=18.1 Hz), 115.78 (d, J=7.6 Hz), 110.62 (d, J=19.6 Hz), 40.40, 27.85. 19F NMR (565 MHz, CDCl3) δ
-129.76. HRMS (ESI): m/z = 247.1241, calcd. for C14H16ON2F ([M+H]+) 247.1247.
N-(5-fluoroquinolin-8-yl)cyclohexanecarboxamide (2q): 30% yield, white solid. 1H NMR (600 MHz,
Chloroform-d) δ 9.70 (s, 1H), 8.87 (dd, J = 4.2, 1.6 Hz, 1H), 8.75 (dd, J = 8.6, 5.4 Hz, 1H), 8.44 (dd, J = 8.4, 1.5
Hz, 1H), 7.53 (dd, J = 8.4, 4.2 Hz, 1H), 7.21 (t, J = 9.2 Hz, 1H), 2.47 (tt, J = 11.8, 3.6 Hz, 1H), 2.13-2.03 (m, 2H),
1.88 (dt, J = 12.9, 3.5 Hz, 2H), 1.64 (m, 3H), 1.39 (m, 2H), 1.32 (m, 1H). 13C NMR (151 MHz, Chloroform-d) δ
174.89, 153.66 (d, J=250.7 Hz), 149.07, 138.81 (d, J=3.0 Hz), 131.31 (d, J=4.5 Hz), 129.95 (d, J=4.5 Hz), 121.75
(d, J=1.5 Hz), 118.91 (d, J=18.1 Hz), 116.01 (d, J=7.5 Hz), 110.65 (d, J=19.6 Hz), 46.97, 29.88, 25.90, 25.89. 19F
NMR (565 MHz, CDCl3) δ -129.68. HRMS (ESI): m/z = 273.1396, calcd. for C16H18ON2F ([M+H]+) 273.1403.
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5-fluoroquinolin-8-amine (2r): 22% yield , yellow solid(a mixture was obtained, the yiled was calculated based on 1H NMR). 1H NMR (600 MHz, Chloroform-d) δ 8.80 (dd, J = 4.2, 1.7 Hz, 1H), 8.09 (dd, J = 8.3, 1.7 Hz, 1H), 7.36
(dd, J = 8.3, 4.2 Hz, 1H), 7.31 (dd, J = 10.5, 8.9 Hz, 1H), 7.13 (dd, J = 8.9, 5.5 Hz, 1H), 4.87 (s, 2H). 13C NMR
(151 MHz, Chloroform-d) 149.46 (d, J=237.1 Hz), 148.36, 139.48 (d, J=9.1 Hz), 136.20, 130.34 (d, J=12.1 Hz),
125.61, 120.50 (d, J=3.0 Hz), 116.99 (d, J=22.6 Hz), 115.47 (d, J=9.1 Hz). 19F NMR (565 MHz, CDCl3) δ
-134.8584. HRMS (ESI): m/z = 163.06660665, calcd. for C9H8N2F ([M+H]+) 163.0672.
References 1. V. G. Zaitsev, D. Shabashov, O. Daugulis, J. Am. Chem. Soc., 2005, 127, 13154. 2. J. Ding, Y. Zhang, J. Li, Org. Chem. Front., 2017, 4, 1528.
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NMR Spectra Images of Starting Substrates and Products
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