The Journal of Organic Chemistry
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Hz), 7.56 (1H, d, J 7.7 Hz), 8.09 (2H, m); 13C NMR (CDCl3) δ 33.6,
41.3, 68.1, 121.5, 121.8, 129.5, 133.0, 147.1; FTIR (υmax cm−1) 2942,
1522, 1348, 1078, 803, 737, 686; Rf 0.56 (30% EtOAc/hexane);
HRMS (ESI+) calculated for C11H13NO3Na [M + Na]+ 230.0788,
found 230.0781.
4.07 (1H, td, J 8.3, 4.5 Hz), 4.15 (1H, t, J 8.0 Hz), 7.14 (2H, d, J 8.4
Hz), 7.16 (2H, d, J 8.5 Hz); 13C NMR (CDCl3) δ 21.0, 34.7, 44.6,
68.5, 74.7, 127.1, 129.3, 136.1, 139.5; FTIR (υmax cm−1) 2971, 1515,
1055, 811, 770; Rf 0.92 (30% EtOAc/hexane); HRMS (ESI+)
calculated for C11H15O [M + H]+ 163.1117, found 163.1118.
3-(4-Methoxyphenyl)tetrahydrofuran (10b). Isolated as a
colorless oil (24.6 mg, 0.138 mmol, 28%) according to general
procedure C: 1H NMR (CDCl3) δ 1.97 (1H, dq, J 12.3, 8.2 Hz), 2.34
(1H, dtd, J 12.2, 7.7, 4.6 Hz), 3.36 (1H, quint., J 7.9 Hz), 3.68 (1H, t, J
8.0 Hz), 3.80 (3H, s), 3.91 (1H, q, J 7.8 Hz), 4.06 (1H, td, J 8.4, 4.5
Hz), 4.12 (1H, t, J 8.0 Hz), 6.86 (2H, d, J 8.6 Hz), 7.17 (2H, d, J 8.8
Hz); 13C NMR (CDCl3) δ 34.7, 44.2, 55.3, 68.5, 74.7, 114.0, 128.2,
134.5, 158.2; FTIR (υmax cm−1) 2934, 1512, 1243, 1178, 1033, 827; Rf
0.77 (30% EtOAc/hexane); HRMS (ESI+) calculated for C11H15O2
[M + H]+ 179.1072, found 179.1076.
4-(p-Tolyl)tetrahydro-2H-thiopyran (8a). Isolated as a white
amorphous solid (75.0 mg, 0.390 mmol, 78%) according to general
procedure C: 1H NMR (CDCl3) δ 1.87 (2H, app. qd, J 12.7, 3.1 Hz),
2.15 (2H, dd, J 13.5, 2.8 Hz), 2.35 (3H, s), 2.51 (1H, tt, J 12.1, 3.1
Hz), 2.72 (2H, br d, J 13.9 Hz), 2.86 (2H, td, J 12.3, 2.3 Hz), 7.12
(2H, d, J 8.1 Hz), 7.15 (2H, d, J 8.2 Hz); 13C NMR (CDCl3) δ 21.0,
29.4, 35.3, 43.9, 126.7, 129.2, 135.8, 144.0; FTIR (υmax cm−1) 2922,
1514, 1109, 951, 816, 658; Rf 0.94 (30% EtOAc/hexane); HRMS (ESI
+) calculated for C12H17S [M + H]+ 193.1045, found 193.1040.
4-(4-Methoxyphenyl)tetrahydro-2H-thiopyran (8b). Isolated
as a white amorphous solid (77.5 mg, 0.372 mmol, 74%) according to
3-(3-Nitrophenyl)tetrahydrofuran (10c). Isolated as a colorless
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general procedure C: H NMR (CDCl3) δ 1.82 (2H, app. qd, J 12.7,
oil (8.9 mg, 0.0461 mmol, 9%) according to general procedure C: H
3.1 Hz), 2.12 (2H, dd, J 13.5, 2.8 Hz), 2.47 (1H, tt, J 12.1, 3.1 Hz),
2.69 (2H, br d, J 13.9 Hz), 2.84 (2H, m), 3.79 (3H, s), 6.85 (2H, d, J
8.5 Hz), 7.11 (2H, d, J 8.6 Hz); 13C NMR (CDCl3) δ 29.4, 35.5, 43.5,
55.3, 113.9, 127.6, 139.2, 158.0; FTIR (υmax cm−1) 2914, 1511, 1245,
1179, 1028, 821; Rf 0.88 (30% EtOAc/hexane); HRMS (ESI+)
calculated for C12H17OS [M + H]+ 209.0995, found 209.0987.
4-(3-Nitrophenyl)tetrahydro-2H-thiopyran (8c). Isolated as a
white amorphous solid (24.7 mg, 0.111 mmol, 22%) according to
NMR (CDCl3) δ 2.03 (1H, dq, J 12.5, 7.8 Hz), 2.46 (1H, dtd, J 12.6,
7.9, 4.7 Hz), 3.53 (1H, quint., J 7.5 Hz), 3.78 (1H, dd, J 8.7, 6.7 Hz),
3.95 (1H, q, J 8.1 Hz), 4.12 (1H, td, J 8.3, 4.6 Hz), 4.16 (1H, dd, J 8.6,
7.3 Hz), 7.49 (1H, t, J 7.9 Hz), 7.59 (1H, br d, J 7.7 Hz, C6), 8.09 (1H,
ddd, J 8.1, 2.1, 1.0 Hz), 8.12 (1H, t, J 1.8 Hz); 13C NMR (CDCl3) δ
34.6, 44.6, 68.4, 74.3, 121.7, 122.2, 129.6, 133.5, 145.2, 148.5; FTIR
(υmax cm−1) 2935, 1523, 1344, 735, 686; Rf 0.49 (30% EtOAc/
hexane); HRMS (ESI+) calculated for C10H11NO3Na [M + Na]+
216.0631, found 216.0626.
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general procedure C: H NMR (CDCl3) δ 1.89 (2H, app. qd, J 12.7,
3.2 Hz), 2.17 (2H, dd, J 13.4, 2.9 Hz), 2.68 (3H, m), 2.86 (2H, td, J
13.1, 2.0 Hz), 7.52 (2H, m), 8.07 (1H, t, J 2.1 Hz), 8.24 (1H, d, J 8.0
Hz); 13C NMR (CDCl3) δ 29.0, 34.9, 44.0, 121.9, 123.5, 129.3, 133.1,
148.6; FTIR (υmax cm−1) 2915, 1511, 1246, 1180, 1029, 954, 821; Rf
0.68 (30% EtOAc/hexane); HRMS (ESI+) calculated for C11H14NO2S
[M + H]+ 224.0740, found 224.0734.
tert-Butyl 3-(p-tolyl)azetidine-1-carboxylate (12a). Isolated as
a colorless oil (80.4 mg, 0.325 mmol, 65%) according to general
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procedure C: H NMR (CDCl3) δ 1.48 (9H, s), 2.35 (3H, s), 3.70
(1H, tt, J 8.7, 6.2 Hz), 3.96 (2H, dd, J 8.4, 6.2 Hz), 4.31 (2H, t, J 8.6
Hz), 7.16 (2H, d, J 8.4 Hz), 7.20 (2H, d, J 8.2 Hz); 13C NMR (CDCl3)
δ 21.0, 28.5, 33.2, 56.5 (br), 79.5, 126.7, 129.4, 136.6, 139.2, 156.5;
FTIR (υmax cm−1) 2970, 1698, 1389, 1128, 811, 772; Rf 0.88 (30%
EtOAc/hexane); HRMS (ESI+) calculated for C15H22NO2 [M + H]+
248.1645, found 248.1645.
tert-Butyl 3-(p-tolyl)pyrrolidine-1-carboxylate (9a). Isolated as
a colorless oil (63.0 mg, 0.241 mmol, 48%) according to general
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procedure C: H NMR (CDCl3, 1:1 mixture of rotamers at room
temperature) δ 1.48 (4.5H, s), 1.49 (4.5H, s), 1.96 (1H, m), 2.23 (1H,
m), 2.33 (3H, s), 3.33 (3H, m), 3.55 (0.5H, br t, J 8.7 Hz), 3.65 (0.5H,
br t, J 8.7 Hz), 3.77 (0.5H, br t, J 8.4 Hz), 3.84 (0.5H, m), 7.13 (4H,
app. s); 13C NMR (CDCl3) δ 21.0, 28.6, 32.5, 33.5, 43.0, 43.9, 45.7,
46.0, 51.9, 52.7, 79.3, 126.9, 129.3, 136.4, 138.4, 154.6; FTIR (υmax
cm−1) 2975, 1693, 1390, 1366, 1159, 1109, 879, 805, 770; Rf 0.91
(30% EtOAc/hexane); HRMS (ESI+) calculated for C16H23NO2Na
[M + Na]+ 284.1626, found 284.1634.
tert-Butyl 3-(4-methoxyphenyl)pyrrolidine-1-carboxylate
(9b). Isolated as a colorless oil (64.2 mg, 0.231 mmol, 46%) according
to general procedure C: 1H NMR (CDCl3, 5:4 mixture of rotamers at
room temperature) δ 1.47 (5H, s), 1.48 (4H, s), 1.94 (1H, m), 2.21
(1H, m), 3.21 (0.6H, t, J 9.9 Hz), 3.28 (1.4H, m), 3.38 (1H, m), 3.54
(0.4H, t, J 8.5 Hz), 3.63 (0.6H, t, J 8.6 Hz), 3.74 (0.6H, dd, J 10.2, 7.8
Hz), 3.79 (3H, s), 3.82 (0.4H, m), 6.86 (2H, d, J 8.7 Hz), 7.15 (2H, d,
J 8.5 Hz); 13C NMR (CDCl3) δ 28.6, 32.6, 33.5, 42.6, 43.5, 45.6, 46.0,
52.0, 52.8, 55.3, 79.2, 114.0, 128.0, 133.4, 154.6, 158.4; FTIR (υmax
cm−1) 2973, 1690, 1514, 1398, 1245, 1164, 1121, 1033, 828, 770; Rf
0.69 (30% EtOAc/hexane); HRMS (ESI+) calculated for
C16H23NO3Na [M + Na]+ 300.1576, found 300.1563.
tert-Butyl 3-(4-methoxyphenyl)azetidine-1-carboxylate
(12b). Isolated as a colorless oil (80.3 mg, 0.305 mmol, 61%)
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according to general procedure C: H NMR (CDCl3) δ 1.46 (9H, s),
3.68 (1H, tt, J 8.7, 6.1 Hz), 3.80 (3H, s), 3.93 (2H, dd, J 8.5, 6.2 Hz),
4.30 (2H, t, J 8.6 Hz), 6.88 (2H, d, J 8.6 Hz), 7.23 (2H, d, J 8.8 Hz);
13C NMR (CDCl3) δ 28.4, 32.9, 55.3, 56.8 (br), 79.5, 114.1, 127.8,
134.3, 156.5, 158.6; FTIR (υmax cm−1) 2969, 1697 (s), 1514, 1390,
1246, 1129, 1033, 826; Rf 0.74 (30% EtOAc/hexane); HRMS (ESI+)
calculated for C15H21NO3Na [M + Na]+ 286.1414, found 286.1402.
tert-Butyl 3-(3-nitrophenyl)azetidine-1-carboxylate (12c).
Isolated as a colorless oil (23.1 mg, 0.0830 mmol, 17%) according
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to general procedure C: H NMR (CDCl3) δ 1.47 (9H, s), 3.84 (1H,
tt, J 8.6, 5.8 Hz), 3.98 (2H, dd, J 8.6, 5.8 Hz), 4.39 (2H, t, J 8.7 Hz),
7.54 (1H, t, J 7.9 Hz), 7.67 (1H, d, J 7.7 Hz), 8.13 (1H, ddd, J 8.2, 2.2,
0.9 Hz), 8.17 (1H, t, J 1.8 Hz); 13C NMR (CDCl3) δ 28.4, 33.2, 56.3
(br), 80.0, 121.9, 122.1, 129.8, 132.9, 144.4, 148.5, 156.3; FTIR (υmax
cm−1) 2976, 1697, 1529, 1130, 735, 684; Rf 0.46 (30% EtOAc/
hexane); HRMS (ESI+) calculated for C14H18N2O4Na [M + Na]+
301.1164, found 301.1164.
3-(p-Tolyl)oxetane (13a). Isolated as a colorless oil (24.6 mg,
0.166 mmol, 33%) according to general procedure C: 1H NMR
(CDCl3) δ 2.36 (3H, s), 4.21 (1H, m), 4.77 (2H, dd, J 6.9, 6.1 Hz),
5.06 (2H, dd, J 8.4, 6.1 Hz), 7.19 (2H, d, J 7.7 Hz), 7.29 (2H, d, J 8.1
Hz); 13C NMR (CDCl3) δ 21.0, 40.0, 79.1, 126.7, 129.4, 136.7, 138.5;
FTIR (υmax cm−1) 2961, 1606, 1515, 1116, 980, 810; Rf 0.86 (30%
EtOAc/hexane); HRMS (ESI+) calculated for C10H12ONa [M + Na]+
171.0780, found 171.0778.
tert-Butyl 3-(3-nitrophenyl)pyrrolidine-1-carboxylate (9c).
Isolated as a colorless oil (8.8 mg, 0.0421 mmol, 8%) according to
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general procedure C: H NMR (CDCl3, 1:1 mixture of rotamers at
room temperature) δ 1.48 (9H, s), 2.02 (1H, m), 2.33 (1H, br), 3.34
(3H, m), 3.59 (0.5H, br t, J 8.4 Hz), 3.67 (0.5H, br t, J 9.0 Hz), 3.83
(1H, m), 7.50 (1H, t, J 8.2 Hz), 7.56 (1H, d, J 7.7 Hz), 8.11 (2H, m);
13C NMR (CDCl3) δ 28.5, 32.4, 33.2, 43.0, 43.9, 45.5, 45.7, 51.7, 52.2,
79.7, 122.0, 122.1, 129.6, 133.3, 143.6, 148.5, 154.4; FTIR (υmax cm−1)
2975, 1688, 1529, 1399, 1346, 1162, 1122, 736; Rf 0.56 (30% EtOAc/
hexane); HRMS (ESI+) calculated for C15H20N2O4Na [M + Na]+
315.1321, found 315.1335.
3-(4-Methoxyphenyl)oxetane (13b). Isolated as a colorless oil
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(35.5 mg, 0.216 mmol, 43%) according to general procedure C: H
NMR (CDCl3) δ 3.81 (3H, s), 4.19 (1H, m), 4.75 (2H, dd, J 6.8, 6.0
Hz), 5.05 (2H, dd, J 8.4, 6.0 Hz), 6.91 (2H, d, J 8.7 Hz), 7.33 (2H, d, J
8.8 Hz); 13C NMR (CDCl3) δ 39.7, 55.3, 79.3, 114.1, 127.9, 133.6,
158.6; FTIR (υmax cm−1) 2957, 1512, 1243, 1178, 977, 911, 826; Rf
0.64 (30% EtOAc/hexane); HRMS (ESI+) calculated for C10H13O2
[M + H]+ 165.0910, found 165.0909.
3-(p-Tolyl)tetrahydrofuran (10a). Isolated as a colorless oil (33.0
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mg, 0.203 mmol, 41%) according to general procedure C: H NMR
(CDCl3) δ 2.01 (1H, dq, J 12.3, 8.2 Hz), 2.36 (4H, m), 3.38 (1H,
quint., J 7.9 Hz), 3.71 (1H, t, J 8.1 Hz), 3.93 (1H, td, J 8.1, 7.3 Hz),
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dx.doi.org/10.1021/jo402526z | J. Org. Chem. XXXX, XXX, XXX−XXX