Beilstein J. Org. Chem. 2011, 7, 1379–1386.
pressure, the crude product was purified by flash column chro- 6.2 Hz, 1H), 2.43 (s, 3H), 2.09 (ddd, J = 17.5, 14.4, 6.1 Hz,
matography on alumina with pentane/ethyl acetate 85:15 as 1H), 1.97–1.76 (m, 1H); 19F NMR (376 MHz, CDCl3) δ −149.5
eluent.
(dd, JH-F = 80.7, JF-F = 8.9 Hz, 1F), −171.6 to −173.7 (m, 1F);
13C NMR (101 MHz, CDCl3) δ 144.8 (C), 142.0 (dd, JC-F =
250.4, 10.1 Hz, CH), 133.3 (C), 129.9 (2CH), 128.2 (C), 127.8
(2CH), 88.1 (dd, JC-F = 178.7, 3.5 Hz, CHF), 48.7 (CH2), 30.4
(d, JC-F = 23.1 Hz, CH2), 21.8 (CH3); IR (neat) 2359, 1597,
1353, 1163, 1133, 1090, 1060, 1011, 964, 814, 664 cm−1;
HRMS (m/z): [M + Na]+ calcd for C12H13F2NO2S, 296.0527;
found, 296.0535.
Spectral data of cyclic products
3a. White solid, mp 102 °C; 1H NMR (400 MHz, CDCl3)
δ 7.73 (d, J = 8.3 Hz, 2H), 7.30 (d, J = 8.1 Hz, 2H), 5.38 (d, J =
5.2 Hz, 1H), 5.09 (ddd, JH-F = 54.6, JH-H = 4.2, 1.9 Hz, 1H),
4.76 (d, J = 6.0 Hz, 1H), 3.88–3.82 (m, 1H), 3.63 (td, J = 9.8,
6.5 Hz, 1H), 2.42 (s, 3H), 2.14–1.87 (m, 2H); 19F NMR
(376.5 MHz, CDCl3) δ −168.4 (m, 1F); 13C NMR (101 MHz,
CDCl3) δ 144.5 (C), 143.2 (d, JC-F = 15.4 Hz, C), 134.2 (C), 3b. Colorless oil; 1H NMR (400 MHz, CDCl3) δ 7.73 (d, J =
129.7 (2CH), 127.6 (2CH), 97.2 (d, JC-F = 8.4 Hz, CH2), 93.7 8.3 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 5.35 (s, 1H), 5.16 (s, 1H),
(d, JC-F = 178.5 Hz, CH), 48.6 (CH2), 29.5 (d, JC-F = 22.3 Hz, 4.70 (dt, JH-F = 49.6 Hz, JH-H = 5.3 Hz, 1H), 3.68–3.54 (m,
CH2), 21.7 (CH3); IR (neat) 2358, 1652, 1338, 1251, 1156, 2H), 2.42 (s, 3H), 1.97–1.81 (m, 2H), 1.73 (m, 1H), 1.61–1.48
1085, 1000, 866, 814, 651 cm−1; HRMS (m/z): [M + Na]+ calcd (m, 1H); 19F NMR (376 MHz, CDCl3) δ −173.4 (m, 1F);
for C12H14FNO2S, 278.0621; found, 278.0632.
13C NMR (101 MHz, CDCl3) δ 143.7 (C), 140.5 (d, JC-F =
19.0 Hz, C), 137.3 (C), 129.7 (2CH), 127.7 (2CH), 110.7 (d,
JC-F = 7.7 Hz, CH2), 88.4 (d, JC-F = 178.6 Hz, CHF), 46.9
(CH2), 30.7 (d, JC-F = 21.7 Hz, CH2), 21.7 (CH3), 20.9 (d, JC-F
= 5.4 Hz, CH2); IR (neat) 1647, 1598, 1451, 1340, 1157, 1098,
1057, 950, 908, 814, 690, 653 cm−1; HRMS (m/z): [M + Na]+
calcd for C13H16FNO2S, 292.0778; found, 292.0776.
5a. Isolated as a minor product in mixture with 3a; 1H NMR
(400 MHz, CDCl3) δ 7.71 (d, J = 8.7 Hz, 2H), 7.32 (d, J =
8.7 Hz, 2H), 5.39–5.37 (m, 1H), 5.22 (d, JH-F = 46.8 Hz, 2H),
3.78 (t, J = 8.9 Hz, 2H), 2.43 (s, 3H), 2.33–2.22 (m, 2H);
19F NMR (376 MHz, CDCl3) δ −213.6 to −213.9 (m, 1F);
13C NMR (101 MHz, CDCl3) δ 144.1 (C), 139.5 (d, JC-F =
20.7 Hz, C), 134.1 (C), 130.1 (2CH), 127.8 (2CH), 115.4 (d,
JC-F = 8.1 Hz, CH), 78.5 (d, JC-F = 167.4 Hz, CH2), 50.4 (CH2),
27.7 (CH2), 21.7 (CH3).
8. White solid, mp 66 °C; 1H NMR (300 MHz, CDCl3) δ 7.74
(d, J = 8.2 Hz, 2H), 7.65 (d, J = 8.1 Hz, 2H), 7.30 (d, J =
5.2 Hz, 2H), 7.28 (d, J = 6.3 Hz, 2H), 5.41 (br s, 1H), 3.89–3.69
(m, 2H), 3.54–3.46 (m, 1H), 3.30–3.23 (m, 3H), 2.66–2.52 (m,
1H), 2.44 (s, 3H), 2.42 (s, 3H), 2.01–1.87 (m, 3H), 1.78–1.58
(m, 2H), 1.41 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 143.9 (C),
142.8 (C), 140.9 (C), 138.8 (C), 134.1 (C), 129.7 (2CH), 129.5
(2CH), 127.8 (2CH), 127.3 (2CH), 119.5 (CH), 68.20 (C), 51.3
(CH2), 49.9 (CH2), 39.6 (CH2), 39.2 (CH2), 27.7 (CH2), 26.6
(CH3), 22.7 (CH2), 21.7 (CH3), 21.6 (CH3); IR (neat) 1452,
1332, 1154, 1089, 1000, 811, 655 cm−1; HRMS (m/z):
[M + Na]+ calcd for C24H30N2O4S2, 497.1539; found,
497.1517.
4a. White solid, mp 68 °C; 1H NMR (400 MHz, CDCl3) δ 7.72
(d, J = 8.3 Hz, 2H), 7.39 (dd, JH-F = 80.7, JH-H = 6.1 Hz, 1H),
7.32 (d, J = 8.1 Hz, 2H), 5.63 (dt, JH-F = 53.8 Hz, JH-H =
3.2 Hz, 1H), 3.83 (t, J = 9.2 Hz, 1H), 3.48 (ddd, J = 11.1, 10.1,
1384