The Journal of Organic Chemistry
Article
NMR (400 MHz, CDCl3) δ 7.03−6.94 (m, 1H), 4.72 (t, J = 8.9 Hz,
1H), 2.29 (d, J = 8.7 Hz, 1H), 2.18 (d, J = 13.0 Hz, 1H), 1.88−1.80
(m, 2H), 1.71−1.64 (m, 2H), 1.31−1.24 (m, 2H), 1.22−1.14 (m, 2H),
1.12−1.05 (m, 1H), 1.00−0.92 (m, 1H); 13C NMR (100 MHz,
CDCl3) δ 148.6−148.5 (m), 146.7−146.9 (m), 146.2−145.9 (m),
144.6−144.5 (m), 123.9 (t, J = 15.0 Hz), 106.3 (t, J = 22.6 Hz), 73.2,
44.9, 31.1, 30.4, 27.6, 27.1, 27.0; 19F NMR (377 MHz, CDCl3) δ
−139.2 (dd, JF = 22.6, 15.1 Hz, 2F), −143.6 (dd, JF = 22.6, 15.1 Hz,
2F); HRMS (ESI) calcd for C13H14F4NaO (M + Na)+ 285.0878,
found 285.0872.
−143.8 (dd, JF = 22.6, 11.3 Hz, 2F); HRMS (ESI) calcd for
C22H15F4NNaO (M + Na)+ 408.0987, found 408.0967.
2,3,5,6-Tetrafluorophenyl-(N-Boc-3-indolyl) Carbinol (3w). White
solid (178 mg, 91% yield): mp 108−109 °C; EA/PE (1:10) as the
eluent; 1H NMR (400 MHz, CDCl3) δ 8.1 (d, J = 8 Hz, 1H), 7.6 (d, J
= 7.8 Hz, 1H), 7.5 (s, 1H), 7.35−7.31 (m, 1H), 7.26−7.22 (m, 1H),
7.08−7.01 (m, 1H), 6.5 (s, 1H), 2.89 (s, 9H), 1.67 (s, 9H); 13C NMR
(100 MHz, CDCl3) δ 149.8, 147.5−147.4 (m), 145.9−145.7 (m),
144.9−144.8 (m), 143.4−143.3 (m), 135.8, 128.3, 125.1, 123.4, 123.1,
121.7 (t, JF = 14.1 Hz), 120.7, 119.4, 115.6, 105.8 (t, JF = 22.3 Hz),
84.5, 62.3, 28.3; 19F NMR (377 MHz, CDCl3) δ −138.3 (dd, JF = 21.7,
13.2 Hz, 2F), −143.6 (dd, JF = 21.8, 13 Hz, 2F); HRMS (ESI) calcd
for C20H17F4NNaO3 (M + Na)+ 418.1042, found 418.1025.
2,3,5,6-Tetrafluorophenyl-(tert-butyl) Carbinol (3q). White solid
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(103 mg, 87% yield): mp 60−61 °C; EA/PE (1:15) as the eluent; H
NMR (400 MHz, CDCl3) δ 7.05−6.96 (m, 1H), 4.81 (d, J = 10.0 Hz,
1H), 2.52−2.48 (m, 1H), 1.00 (s, 9H); 13C NMR (100 MHz, CDCl3)
δ 147.5−147.4 (m), 145.7−145.5 (m), 144.9−144.7 (m), 143.3−143.2
(m), 121.4 (t, J = 14.5 Hz), 105.1 (t, J = 22.4 Hz), 76.2, 37.4, 25.8; 19F
NMR (377 MHz, CDCl3) δ −140.0 (dd, JF = 18.9, 7.5 Hz, 2F),
−140.9 (dd, JF = 18.9, 11.3 Hz, 2F); HRMS (ESI) calcd for
C11H12F4NaO (M + Na)+ 259.0722, found 259.0718.
2,3,5,6-Tetrafluoro-4-methoxyphenyl-(2-naphthyl) Carbinol (5a).
White solid (135 mg, 80% yield): mp 69−70 °C; EA/PE (1:10) as the
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eluent; H NMR (400 MHz, CDCl3) δ 7.87 (s, 1H), 7.85−7.83 (m,
3H), 7.51−7.48 (m, 3H), 6.37 (d, J = 6.4 Hz, 1H), 4.07 (s, 3H), 2.93
(d, J = 6.8 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 146.4−146.1
(m), 143.9−143.7 (m), 142.4−142.2 (m), 139.9−139.8 (m), 138.6,
138.3−138.1 (m), 133.3, 133.1, 128.7, 128.3, 127.8, 126.6, 126.4,
124.2, 123.6, 115.1 (t, JF = 15.2 Hz), 67.8, 62.2 (t, JF = 3.7 Hz); 19F
NMR (566 MHz, CDCl3) δ −144.7 to −144.8 (m, 2F), −157.5 (dd, JF
= 20.9, 7.4 Hz, 2F); HRMS (ESI) calcd for C18H12F4NaO (M + Na)+
343.0722, found 343.0731.
2,3,5,6-Tetrafluorophenyl-[(E)-2-phenylvinyl] Carbinol (3r). Col-
orless oil (132 mg, 94% yield): EA/PE (1:10) as the eluent; 1H NMR
(400 MHz, CDCl3) δ 7.41 (d, J = 1.3 Hz, 2H), 7.35−7.26 (m, 3H),
7.07−6.98 (m, 1H), 6.69 (d, J = 15.9 Hz, 1H), 6.54 (dd, J = 15.8, 6.8
Hz, 1H), 5.77 (t, J = 7 Hz, 1H), 2.44 (d, J = 4.1 Hz, 1H); 13C NMR
(100 MHz, CDCl3) δ 147.5−147.4 (m), 145.7−146.6 (m), 145.3−
145.0 (m), 143.1−142.8 (m), 135.9, 132.9, 128.8, 128.0, 127.7, 126.9,
121.9 (t, JF = 14.7 Hz), 105.6 (t, JF = 22.3 Hz), 67.5; 19F NMR (377
MHz, CDCl3) δ −138.6 (dd, JF = 21.6, 13.2 Hz, 2F), −144.1 (dd, JF =
21.5, 13.1 Hz, 2F); HRMS (ESI) calcd for C15H10F4NaO (M + Na)+
305.0565, found 305.0576.
2,3,5,6-Tetrafluoro-4-tert-butyldimethylsilylphenyl-(2-naphthyl)
Carbinol (5b). White solid (174 mg, 83% yield): mp 91−92 °C; EA/
PE (1:10) as the eluent; 1H NMR (400 MHz, CDCl3) δ 7.91 (s, 1H),
7.87−7.83 (m, 3H), 7.55−7.49 (m, 3H), 6.43 (s, 1H), 3.01 (s, 1H),
0.95 (s, 9H), 0.4 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 150.6−
150.5 (m), 148.3−148.1 (m), 145.5−145.3 (m), 143.0−142.8 (m),
138.4, 133.3, 133.2, 128.8, 128.3, 127.8, 126.6, 126.5, 124.4, 123.7,
123.3 (t, JF = 14.7 Hz), 114.8 (t, JF = 32.8 Hz), 68.4, 26.3, 17.8, −3.9
(t, JF = 4.5 Hz); 19F NMR (377 MHz, CDCl3) δ −124.7 (dd, JF = 24.2,
14.8 Hz, 2F), −143.7 (dd, JF = 23.5, 14.1 Hz, 2F); HRMS (ESI) calcd
for C23H24F4NaOSi (M + Na)+ 443.1430, found 443.1439.
2,3,5,6-Tetrafluorophenyl-(3-thiophenyl) Carbinol (3s). White
solid (125 mg, 96% yield): mp 39−40 °C; EA/PE (1:10) as the
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eluent; H NMR (400 MHz, CDCl3) δ 7.34−7.32 (m, 1H), 7.23 (s,
1H), 7.08−7.06 (m, 1H), 7.04−6.99 (m, 1H), 6.26 (s, 1H), 2.83 (br,
1H); 13C NMR (100 MHz, CDCl3) δ 147.5−147.2 (m), 145.6−145.4
(m), 145.0−144.8 (m), 143.2−142.9 (m), 142.1, 126.9, 125.8, 122.4
(t, JF = 14.2 Hz), 121.9, 105.6 (t, JF = 22.5 Hz), 65.0; 19F NMR (566
MHz, CDCl3) δ −138.5 (dd, JF = 21.6, 12.6 Hz, 2F), −149.9 (dd, JF =
22.0, 13.6 Hz, 2F); HRMS (ESI) calcd for C11H6F4NaOS (M + Na)+
284.9973, found 284.9966.
2,3,5,6-Tetrafluoro-4-benzylphenyl-(2-naphthyl) Carbinol (5c).
White solid (171 mg, 87% yield): mp 78−79 °C; EA/PE (1:10) as
the eluent; 1H NMR (400 MHz, CDCl3) δ 7.76 (s, 1H), 7.72−7.7 (m,
3H), 7.38−7.36 (m, 3H), 7.2−7.1 (m, 5H), 6.28 (d, J = 6.9 Hz, 1H),
3.93 (s, 2H), 2.74 (d, J = 7.1 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ
146.3−146.1 (m), 145.9−145.8 (m), 143.8−143.7 (m), 143.5−143.1
(m), 138.4, 137.7, 133.3, 133.1, 128.9, 128.7, 128.6, 128.3, 127.8,
127.0, 126.6, 126.5, 124.3, 123.7, 120.0 (t, JF = 14.6 Hz), 119.5 (t, JF =
18.4 Hz), 68.1, 28.8; 19F NMR (377 MHz, CDCl3) δ −143.31 (dd, JF
= 22.3, 12.7 Hz, 2F), −144.0 (dd, JF = 21.9, 12.4 Hz, 2F); HRMS
(ESI) calcd for C24H16F4NaO (M + Na)+ 419.1035, found 419.1009.
2,3,5,6-Tetrafluoro-4-methylphenyl-(2-naphthyl) Carbinol (5d).
White solid (126 mg, 91% yield): mp 112−113 °C; EA/PE (1:10)
2,3,5,6-Tetrafluorophenyl-(4-pyridyl) Carbinol (3t). White solid
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(116 mg, 90% yield): mp 45−46 °C; EA/PE (1:5) as the eluent; H
NMR (400 MHz, d6-DMSO) δ 8.53 (d, J = 5.8 Hz, 2H), 7.86−7.77
(m, 1H), 7.38 (d, J = 5.3 Hz, 2H), 6.78 (d, J = 4 Hz, 1H), 6.15 (d, J =
4 Hz, 1H); 13C NMR (100 MHz, d6-DMSO) δ 150.9, 149.6, 146.9−
146.7 (m), 145.4−145.2 (m), 144.5−144.2 (m), 142.9−142.7 (m),
122.7 (t, JF = 15.3 Hz), 120.6, 106.6 (t, JF = 23.3 Hz), 64.0; 19F NMR
(566 MHz, d6-DMSO) δ −139.2 to −139.3 (m, 2F), −143.1 to
−143.2 (m, 2F); HRMS (ESI) calcd for C12H7F4NNaO (M + Na)+
280.0361, found 280.0379.
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as the eluent; H NMR (400 MHz, CDCl3) δ 7.88−7.82 (m, 4H),
7.51−7.49 (m, 3H), 6.4 (d, J = 8 Hz, 2H), 3.09 (d, J = 7.6 Hz, 1H),
2.26 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 146.1−146.0 (m),
145.1−145.0 (m), 144.5−144.4 (m), 143.5−143.4 (m), 138.6, 133.3,
133.1, 128.7, 128.3, 127.8, 126.5, 126.4, 124.3, 123.7, 119.1 (t, JF = 15
Hz), 116.0 (t, JF = 18.9 Hz), 68.0, 7.6; 19F NMR (377 MHz, CDCl3) δ
−143.3 (dd, JF = 21.7, 12.5 Hz, 2F), −145.2 (dd, JF = 21.9, 12.6 Hz,
2F); HRMS (ESI) calcd for C18H12F4NaO (M + Na)+ 343.0722,
found 343.0731.
2,3,5,6-Tetrafluorophenyl-(4-quinolinyl) Carbinol (3u). White
solid (116 mg, 93% yield): mp 45−46 °C; EA/PE (1:5) as the
eluent; 1H NMR (400 MHz, d6-DMSO) δ 9.0 (d, J = 3.6 Hz), 8.1 (d, J
= 8.3 Hz), 7.9 (s, 1H), 7.9−7.8 (m, 1H). 7.8 (d, J = 8.4 Hz), 7.7 (t, J =
7.2 Hz), 7.6 (t, J = 7.4 Hz), 6.9 (s, 1H), 6.8 (s, 1H); 13C NMR (100
MHz, d6-DMSO) δ 150.3, 147.7, 146.1, 144.8−144.7 (m), 143.9−
143.7 (m), 139.0, 129.0, 127.0, 124.6, 122.3, 122.1−122 (m), 118.8,
106.7 (t, JF = 22.9 Hz), 62.0; 19F NMR (377 MHz, d6-DMSO) δ
−138.9 (dd, JF = 22.6, 11.3 Hz, 2F), −142.6 (dd, JF = 22.6, 11.3 Hz,
2F); HRMS (ESI) calcd for C16H10F4NO (M + H)+ 308.0699, found
308.0679.
2,3,5,6-Tetrafluorophenyl-(N-benzyl-3-indolyl) Carbinol (3v).
White solid (162 mg, 84% yield): mp 101−102 °C; EA/PE (1:10)
as the eluent; 1H NMR (400 MHz, CDCl3) δ 7.72 (d, J = 7.7 Hz, 1H),
7.27−7.14 (m, 5H), 7.06 (d, J = 6.8 Hz, 2H), 7.0 (s, 2H), 6.6 (s, 1H),
5.24 (s, 2H), 2.71 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 147.5−
147.4 (m), 145.9−145.8 (m), 145.1−144.8 (m), 143.5−143.4 (m),
137.2, 137.1, 129.0, 127.9, 126.8, 126.4, 126.3, 122.9 (t, JF = 14.2 Hz),
122.7, 120.3, 119.5, 115.6, 110.3, 105.3 (t, JF = 22.6 Hz), 62.7, 50.4;
19F NMR (377 MHz, CDCl3) δ −138.7 (dd, JF = 22.6, 15.1 Hz, 2F),
2,3,5,6-Tetrafluoro-4-methoxymethylphenyl-(2-naphthyl) Carbi-
nol (5e). Colorless oil (152 mg, 87% yield): EA/PE (1:10) as the
eluent; 1H NMR (400 MHz, CDCl3) δ 7.87−7.82 (m, 4H), 7.51−7.49
(m, 3H), 6.41 (d, J = 6.8 Hz, 1H), 4.56 (s, 2H), 3.39 (s, 3H), 3.17 (d, J
= 7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 146.9−146.7 (m),
145.5−145.4 (m), 144.3−144.0 (m), 143.1−142.9 (m), 138.2, 133.2,
133.1, 128.7, 128.2, 127.8, 126.6, 126.4, 124.3, 123.6, 122.3 (t, JF =
14.5 Hz), 115.7 (t, JF = 17.6 Hz), 68.0, 61.5, 58.6; 19F NMR (377
MHz, CDCl3) δ −143.2 (dd, JF = 22.9, 13.8 Hz, 2F), −143.6 (dd, JF =
21.6, 12.6 Hz, 2F); HRMS (ESI) calcd for C19H14F4NaO2 (M + Na)+
373.0828, found 373.0831.
2,3,5,6-Tetrafluoro-4-allylphenyl-(2-naphthyl) Carbinol (5f). Yel-
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low oil (160 mg, 92% yield): EA/PE (1:10) as the eluent; H NMR
F
J. Org. Chem. XXXX, XXX, XXX−XXX