The Journal of Organic Chemistry
Note
Hz, 2H), 7.49 (d, J = 8.0 Hz, 2H), 7.17 (t, J = 7.25 Hz, 1H), 7.12−7.09
(m, 2H), 7.01 (d, J = 7.5 Hz, 2H), 5.92 (d, J = 9.0 Hz, 1H), 4.58 (q, J
= 4.5 Hz, 1H), 4.48−4.43 (m, 1H), 1.55 (d, J = 7.0 Hz, 3H); 13C
NMR (125 MHz, CDCl3) δ 143.5, 135.1, 134.0 (q, J = 32.7 Hz),
128.3, 128.1 (4C), 127.8 (2C), 127.5 (2C), 125.7 (q, J = 3.8 Hz), 62.6,
53.3, 22.2; HRMS (ESI) calcd for C16H1579BrF3NNaO2S m/z [M +
Na]+ 443.9851, found 443.9848; Rf = 0.37 (hexane/EtOAc = 3:1).
N-(2-Bromo-1,2-diphenylethyl)-4-(trifluoromethyl)-
benzenesulfonamide (2h). 61 mg, 57%; yellow solid, mp 168.2−169.8
°C; IR (KBr) 3280, 1456, 1419, 1326, 1166, 1130, 1063, 839, 699,
(d, J = 8.5 Hz, 2H), 4.87 (d, J = 5.5 Hz, 1H), 3.79 (td, J = 4.0, 10.5 Hz,
1H), 3.22−3.20 (m, 1H), 2.36−2.30 (m, 2H), 1.80 (qd, J = 3.5, 11.5
Hz, 1H), 1.72−1.68 (m, 2H), 1.56 (m, 1H), 1.37−1.25 (m, 2H); 13C
NMR (75 MHz, CDCl3) δ 143.7, 134.4 (q, J = 34.0 Hz), 127.9 (4C),
126.1 (q, J = 3.8 Hz), 59.4, 54.8, 36.4, 34.0, 25.7, 23.8; HRMS (ESI)
calcd for C13H1579BrF3NNaO2S m/z [M + Na]+ 407.9851, found
407.9863; Rf = 0.33 (hexane/EtOAc = 3:1).
N-(2-Bromocycloheptyl)-4-(trifluoromethyl)benzenesulfonamide
(2n). 80 mg, 91%; white solid, mp 108.5−110.0 °C; IR (KBr) 3249,
2926, 2860, 1455, 1404, 1324, 1161, 1142, 1061, 940, 863, 841, 714,
657, 630, 599, 426 cm−1; 1H NMR (500 MHz, CDCl3) δ 8.03 (d, J =
8.0 Hz, 2H), 7.79 (d, J = 8.5 Hz, 2H), 4.94 (d, J = 6.5 Hz, 1H), 3.99
(td, J = 3.5, 7.5 Hz, 1H), 3.52−3.50 (m, 1H), 2.17−2.05 (m, 2H),
1.67−1.61 (m, 5H), 1.54−1.49 (m, 3H); 13C NMR (125 MHz,
CDCl3) δ 143.6, 134.4 (q, J = 32.7 Hz), 127.9 (4C), 126.1 (q, J = 3.8
Hz), 62.9, 58.3, 35.0, 32.2, 27.2, 24.0, 22.9; HRMS (ESI) calcd for
C14H1779BrF3NNaO2S m/z [M + Na]+ 422.0008, found 422.0016; Rf =
0.34 (hexane/EtOAc = 3:1).
1
610, 534, 430 cm−1; H NMR (300 MHz, CDCl3) δ 7.58 (d, J = 8.1
Hz, 2H), 7.45 (d, J = 8.4 Hz, 2H), 7.28−7.22 (m, 3H), 7.17−7.04 (m,
5H), 6.67 (d, J = 7.5 Hz, 2H), 5.21−5.17 (m, 2H), 4.91−4.86 (m,
1H); 13C NMR (75 MHz, CDCl3) δ 143.4, 136.7, 135.9, 129.0, 128.6,
128.5, 128.3, 128.2, 128.0, 127.9, 127.5, 127.4, 125.6 (q, J = 3.8 Hz),
63.3, 57.3; HRMS (ESI) calcd for C21H1779BrF3NNaO2S m/z [M +
Na]+ 506.0008, found 506.0007; Rf = 0.35 (hexane/EtOAc = 3:1).
N-(3R,4R)-(4-Bromohexan-3-yl)-4-(trifluoromethyl)-
benzenesulfonamide (2i). 78 mg, 92%; white solid, mp 85.2−87.2 °C;
IR (KBr) 3276, 2974, 1462, 1420, 1323, 1182, 1063, 1001, 906, 843,
N-(2-Bromocyclooctyl)-4-(trifluoromethyl)benzenesulfonamide
(2o). 84 mg, 92%; white solid, mp 110.1−112.1 °C; IR (KBr) 3251,
2930, 2870, 1445, 1404, 1322, 1166, 1060, 842, 811, 713, 668, 640,
1
711, 609, 430 cm−1; H NMR (300 MHz, CDCl3) δ 8.01 (d, J = 8.1
1
599, 426 cm−1; H NMR (500 MHz, CDCl3) δ 8.02 (d, J = 8.5 Hz,
Hz, 2H), 7.79 (d, J = 8.4 Hz, 2H), 4.76 (d, J = 9.6 Hz, 1H), 4.02−3.97
(m, 1H), 3.35−3.31 (m, 1H), 1.82−1.45 (m, 4H), 0.98 (t, J = 7.2 Hz,
3H), 0.76 (t, J = 7.2 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 145.0,
134.3 (q, J = 32.7 Hz), 127.3 (4C), 126.2 (q, J = 3.8 Hz), 62.1, 59.3,
29.3, 27.8, 12.5, 10.4; HRMS (ESI) calcd for C13H1779BrF3NNaO2S
m/z [M + Na]+ 410.0008, found 410.0014; Rf = 0.47 (hexane/EtOAc
= 3:1).
2H), 7.79 (d, J = 8.0 Hz, 2H), 4.85 (d, J = 5.0 Hz, 1H), 4.05−4.01 (m,
1H), 3.56−3.51 (m, 1H), 2.29−2.23 (m, 1H), 2.15−2.10 (m, 1H),
2.06−1.99 (m, 1H), 1.82−1.63 (m, 5H), 1.56−1.49 (m, 2H); 13C
NMR (125 MHz, CDCl3) δ 143.3, 134.4 (q, J = 32.7 Hz), 128.0 (4C),
126.0 (q, J = 3.8 Hz), 61.5, 59.1, 32.4, 32.4, 25.6, 25.4, 25.4, 25.0;
HRMS (ESI) calcd for C15H1979BrF3NNaO2S m/z [M + Na]+
436.0164, found 436.0169; Rf = 0.38 (hexane/EtOAc = 3:1).
N-(2-Bromo-2,3-dihydro-1H-inden-1-yl)-4-(trifluoromethyl)-
benzenesulfonamide (2p).5f 79 mg, 86%; white solid, mp 160.4−
162.1 °C; IR (KBr) 3271, 2960, 1467, 1338, 1163, 1067, 934, 840,
736, 715, 615, 547, 430 cm−1; 1H NMR (500 MHz, CDCl3) δ 8.11 (d,
J = 8.0 Hz, 2H), 7.83 (d, J = 8.0 Hz, 2H), 7.32−7.29 (m, 1H), 7.24−
7.18 (m, 3H), 5.01−4.98 (m, 1H), 4.93 (d, J = 8.5 Hz, 1H), 4.25 (q, J
= 6.5 Hz, 1H), 3.55 (dd, J = 7.0, 16.5 Hz, 1H), 3.21 (dd, J = 6.5, 16.5
Hz, 1H); 13C NMR (75 MHz, CDCl3) δ 144.0, 139.9, 139.0, 134.6 (q,
J = 32.5 Hz), 129.4, 127.9 (4C), 127.9, 126.3 (q, J = 3.8 Hz), 124.7,
124.3, 67.3, 31.2, 40.9; HRMS (ESI) calcd for C16H1279BrF3NO2S m/z
[M − H]− 417.9730, found 417.9729; Rf = 0.43 (hexane/EtOAc =
3:1).
N-(3R,4S)-(4-Bromohexan-3-yl)-4-(trifluoromethyl)-
benzenesulfonamide (2j). 84 mg, 99%; white solid, mp 81.3−82.9 °C;
IR (KBr) 3291, 2971, 1462, 1418, 1320, 1173, 1062, 1012, 844, 712,
1
617, 541, 429 cm−1; H NMR (500 MHz, CDCl3) δ 8.02 (d, J = 8.5
Hz, 2H), 7.79 (d, J = 8.5 Hz, 2H), 4.90 (d, J = 10.0 Hz, 1H), 3.90−
3.86 (m, 1H), 3.23 (tt, J = 3.0, 9.9 Hz, 1H), 1.79−1.75 (m, 2H), 1.61−
1.47 (m, 3H), 0.98 (t, J = 7.0 Hz, 3H), 0.78 (t, J = 7.0 Hz, 3H); 13C
NMR (75 MHz, CDCl3) δ 144.7, 134.4 (q, J = 33.2 Hz), 127.4 (4C),
126.2 (q, J = 3.7 Hz), 64.9, 59.5, 29.1, 23.1, 12.7, 10.2; HRMS (ESI)
calcd for C13H1779BrF3NNaO2S m/z [M + Na]+ 410.0008, found
410.0005; Rf = 0.54 (hexane/EtOAc = 3:1).
N-(1-Bromooctan-2-yl)-4-(trifluoromethyl)benzenesulfonamide
(2k) and N-(2-Bromooctyl)-4-(trifluoromethyl)benzenesulfonamide
(2k′). 50 mg, 55% (2k:2k′ = 1:1); yellow solid, mp 60.9−62.0 °C; IR
(KBr) 3300, 2931, 2857, 1407, 1324, 1171, 1133, 1109, 1063, 842,
712, 603, 430 cm−1; 1H NMR (CDCl3, 500 MHz) (1) 2k δ 8.03−8.00
(m, 2H), 7.81−7.79 (m, 2H), 5.12 (t, J = 6.2 Hz, 1H), 4.02−3.97 (m,
1H), 3.47−3.37 (m, 2H), 1.77 (q, J = 7.5 Hz, 2H), 1.30−1.25 (m,
4H), 1.21−1.14 (m, 4H), 0.89−0.82 (m, 3H); (2) 2k′ δ 8.03−8.00
(m, 2H), 7.81−7.79 (m, 2H), 4.93 (d, J = 8.7 Hz, 1H), 3.47−3.37 (m,
2H), 3.25−3.19 (m, 1H), 1.57−1.44 (m, 3H), 1.30−1.25 (m, 4H),
1.21−1.14 (m, 3H), 0.89−0.82 (m, 3H); 13C NMR (125 MHz,
CDCl3) δ 144.4, 143.6, 134.6 (q, J = 34.0 Hz), 134.5 (q, J = 34.0 Hz),
127.5 (8C), 126.4 (q, J = 3.8 Hz), 126.3 (q, J = 3.8 Hz), 55.3, 53.7,
49.6, 38.1, 36.0, 33.6, 31.5, 28.6, 28.5, 27.2, 25.3, 22.5, 22.4, 14.0, 13.9;
HRMS (ESI) calcd for C15H2179BrF3NNaO2S m/z [M + Na]+
438.0326, found 438.0333; Rf = 0.52 (hexane/EtOAc = 3:1).
N-((3S, 5R)-2-Bromo-3, 5-dihydroxycyclopentyl)-4-
(trifluoromethyl)benzenesulfonamide (2q). 59 mg, 66%; white solid,
mp 116.7−117.9 °C; [α]2D5 −9.8 (c 1.0, MeOH); IR (KBr) 3358, 2978,
2924, 1718, 1599, 1456, 1396, 1298, 1231, 1150, 1113, 965, 843, 812,
1
694, 598, 534 cm−1; H NMR (500 MHz, MeOD) δ 8.10 (d, J = 8.5
Hz, 2H), 7.86 (d, J = 8.5 Hz, 2H), 3.98−3.96 (m, 1H), 3.91−3.83 (m,
3H), 2.36−2.30 (m, 1H), 1.77−1.73 (m, 1H); 13C NMR (125 MHz,
MeOD) δ 147.2, 134.8 (q, J = 32.7 Hz), 129.1 (4C), 127.1 (q, J = 3.8
Hz), 75.5, 71.0, 69.3, 58.2, 40.5; HRMS (ESI) calcd for
C12H1379BrF3NNaO4S m/z [M + Na]+ 425.9593, found 425.9596; Rf
= 0.34 (CHCl3/MeOH = 8:1).
N-((3S,10R,13S)-5-Bromo-3-((tert-butyldimethylsilyl)oxy)-10,13-
dimethyl-17-oxohexadecahydro-1H-cyclopenta[a]phenanthren-6-
yl)-4-(trifluoromethyl)benzenesulfonamide (2r). 127 mg, 82%; white
solid, mp 150.1−152.1 °C; [α]2D5 −4.5 (c 1.0, CHCl3); IR (KBr) 2952,
2859, 1741, 1472, 1444, 1406, 1324, 1254, 1171, 1139, 1096, 867, 836,
777, 713, 606, 429 cm−1; 1H NMR (300 MHz, CDCl3) δ 8.06 (d, J =
8.1 Hz, 2H), 7.81 (d, J = 8.1 Hz, 2H), 5.92 (d, J = 9.6 Hz, 1H), 4.31−
4.29 (m, 1H), 3.75−3.73 (m, 1H), 2.41−2.32 (dd, J = 7.8, 19.1 Hz,
1H), 2.27−2.19 (m, 2H), 2.05−2.03 (m, 1H), 1.99−1.89 (m, 1H),
1.76−1.71 (m, 3H), 1.64−1.53 (m, 6H), 1.31−1.22 (m, 8H), 0.86 (s,
9H), 0.78 (s, 3H), 0.02 (s, 6H); 13C NMR (125 MHz, CDCl3) δ
143.7, 134.7 (q, J = 34.0 Hz), 127.8 (4C), 126.4, 86.7, 69.1, 60.3, 58.2,
50.0, 47.7, 47.3, 43.3, 41.1, 36.0, 35.5, 31.1, 31.0, 30.6, 30.1, 25.7 (3C),
21.2, 20.3, 18.4, 18.0, 14.1, 13.7, −4.8, −4.8; HRMS (ESI) calcd for
C32H4779BrF3NNaO4SSi m/z [M + Na]+ 728.2023, found 728.2036; Rf
= 0.27 (hexane/EtOAc = 3:1).
N-(2-Bromocyclopentyl)-4-(trifluoromethyl)benzenesulfonamide
(2l). 80 mg, 98%; white solid, mp 123.8−125.6 °C; IR (KBr) 3270,
2974, 1450, 1406, 1322, 1170, 1139, 1061, 922, 839, 712, 602, 558,
1
493, 430 cm−1; H NMR (300 MHz, CDCl3) δ 8.05 (d, J = 8.1 Hz,
2H), 7.81 (d, J = 8.4 Hz, 2H), 5.19 (d, J = 6.3 Hz, 1H), 4.05 (q, J = 6.0
Hz, 1H), 3.72 (quintet, J = 6.0 Hz, 1H), 2.30−2.17 (m, 2H), 2.01−
1.92 (m, 1H), 1.87−1.67 (m, 2H), 1.50−1.40 (m, 1H); 13C NMR (75
MHz, CDCl3) δ 143.5, 134.6 (q, J = 33.2 Hz), 127.8 (4C), 126.4 (q, J
= 3.8 Hz), 63.2, 53.5, 34.0, 30.9, 21.3; HRMS (ESI) calcd for
C12H1379BrF3NNaO2S m/z [M + Na]+ 393.9695, found 393.9707; Rf =
0.35 (hexane/EtOAc = 3:1).
N-(2-Bromocyclohexyl)-4-(trifluoromethyl)benzenesulfonamide
(2m). 38 mg, 45%; white solid, mp 137.1−138.8 °C; IR (KBr) 3270,
2937, 1451, 1405, 1329, 1166, 1090, 1060, 841, 715, 624, 551, 432
Synthesis of 2-Phenylmorpholine (7).14,17 The formation of
aziridine 5 was effected by treatment of bromoamide 2a (820 mg,
1
cm−1; H NMR (500 MHz, CDCl3) δ 8.03 (d, J = 8.5 Hz, 2H), 7.79
E
J. Org. Chem. XXXX, XXX, XXX−XXX