10.1002/ejoc.201900589
European Journal of Organic Chemistry
FULL PAPER
colourless viscous oil, 0.09 g, yield: 64%, Rf value: 0.40 (EtOAc/hexane) =
5:5 (v/v).
g, 0.98 mmol), colorless viscous oil, 0.21 g, yield: 82%, Rf value: 0.40
(EtOAc/hexane) = 4:6 (v/v).
(3c). 1H-NMR (400 MHz): δ 7.33 (d, J = 8.7 Hz, 2H), 6.85 (d, J = 8.7 Hz,
2H), 4.09–3.99 (m, 2H), 4.02 (d, J = 7.0 Hz, 1H), 3.79 (s, 3H), 3.68 (d, J =
7.5 Hz, 1H), 3.20 (s, 3H), 1.07 (t, J = 7.3 Hz, 3H). 13C-NMR (100 MHz): δ
164.5, 160.0, 128.9, 128.2, 122.9, 113.9, 61.9, 55.4, 44.7, 43.7, 40.0, 14.0.
IR (neat): 2934, 2840, 1748, 1612, 1584, 1515, 1463, 1445, 1374, 1322,
1250, 1200, 1149, 1029, 953, 897, 819, 708, 513 cm˗1. HRMS (ESI, Q-
TOF) m/z: [M + H]+ calculated for C13H17NO5SNa 322.0725, found
322.0752.
(7a). 1H-NMR (400 MHz): δ 7.93 (d, J = 8.4 Hz, 2H), 7.26 (d, J = 8.2 Hz,
2H), 4.56 (d, J = 8.5 Hz, 1H), 4.06 – 4.03 (m, 1H), 3.80 (s, 3H), 3.76 (s,
3H), 3.61–3.55 (m, 1H), 2.84 (dd, J = 12.1, 5.6 Hz, 1H), 2.40 (s, 3H), 2.11
(dd, J = 14.5, 11.9 Hz, 1H), 1.96 –1.92 (m, 1H), 1.66 –1.52 (m, 3H), 1.48
–1.39 (m, 1H). 13C-NMR (100 MHz): δ 170.2, 169.3, 143.4, 138.6, 129.0,
128.9, 128.6, 127.8, 95.1, 74.1, 67.6, 53.7, 53.3, 41.5, 37.9, 26.8, 24.8,
21.7. IR (neat): 2951, 2856, 1739, 1597, 1458, 1433, 1342, 1280, 1255,
1159, 1136, 1111, 1066, 1041, 977, 923, 808, 732, 704, 671, 588, 545,
464 cm˗1. HRMS (ESI, Q-TOF) m/z: [M + H]+ calculated for C18H24NO7S
398.1273, found 398.1260.
Diethyl 4-(thiophen-2-yl)-1-tosylazetidine-2,2-dicarboxylate (5a).
Reaction time: 7 h, 4a (0.20 g, 0.74 mmol), 2a (0.30 g, 1.11 mmol), yellow
viscous oil, 0.22 g, yield: 68%, Rf value: 0.35 (EtOAc/hexane) = 2:8 (v/v).
Dimethyl 6-tosylhexahydro-5H-furo[2,3-b]pyrrole-5,5-dicarboxylate
(7b). Reaction time: 8 h, 6d (0.15 g, 0.70 mmol), 2a (0.29 g, 1.05 mmol),
colorless viscous oil, 0.20 g, yield: 74%, Rf value: 0.26 (EtOAc/hexane) =
3:7 (v/v).
(5a). 1H-NMR (400 MHz): δ 7.48 (d, J = 8.2 Hz, 2H), 7.22 (d, J = 5.0 Hz,
1H), 7.10 (d, J = 8.1 Hz, 2H), 7.03 (d, J = 3.9 Hz, 1H), 6.90 (dd, J = 5.4,
3.7 Hz, 1H), 5.92 (t, J = 7.8 Hz, 1H), 4.45–4.37 (m, 2H), 4.32–4.20 (m, 2H),
3.09 (dd, J = 11.7, 8.5 Hz, 1H), 2.64 (dd, J = 11.8, 7.2 Hz, 1H), 2.34 (s,
3H), 1.42 (t, J = 7.1 Hz, 3H), 1.23 (t, J = 7.0 Hz, 3H). 13C-NMR (100 MHz):
δ 168.9, 168.4, 143.7, 143.2, 138.5, 128.9, 127.4, 127.1, 126.8. 126.6,
70.3, 63.1, 62.1, 57.8, 35.6, 21.6, 14.1, 14.0. IR (neat): 2981, 1732, 1598,
1440, 1369, 1340, 1290, 1155, 1091, 1018, 972, 852, 812, 763, 705, 678,
596, 543, 518 cm˗1. HRMS (ESI, Q-TOF) m/z: [M + Na]+ calculated for
C20H23NO6S2Na 460.0864, found 460.0825.
(7b). 1H-NMR (400 MHz): δ 7.90 (d, J = 8.1 Hz, 2H), 7.27 (d, J = 6.5 Hz,
2H), 5.91 (d, J = 6.0 Hz, 1H), 3.86 (s, 3H), 3.82–3.75 (m, 1H), 3.74 (s, 3H),
3.60–3.54 (m, 1H), 3.00–2.93 (m, 1H), 2.71 (dd, J = 13.7, 8.6 Hz, 1H), 2.41
(s, 3H), 2.34 (dd, J = 12.9, 7.7 Hz, 1H), 2.00 –1.90 (m, 1H), 1.61 –1.57 (m,
1H). 13C-NMR (100 MHz): δ 169.9, 168.9, 143.2, 138.9, 129.0, 128.0,
127.9, 95.8, 75.4, 66.1, 53.6, 53.3, 41.0, 40.4, 31.8, 21.7. IR (neat): 2953,
1739, 1597, 1435, 1340, 1267, 1242, 1155, 1070, 1031, 875, 813, 732,
704, 669, 586, 576, 542 cm˗1. HRMS (ESI, Q-TOF) m/z: [M + H]+ calculated
for C17H22NO7S 384.1117, found 384.1093.
Ethyl
4-(4-methoxyphenyl)-1-tosylazetidine-2-carboxylate
(5b).
Reaction time: 12 h, 4b (0.30 g, 1.36 mmol), 2a (0.57 g, 2.04 mmol), yellow
viscous oil, 0.29 g (trans: cis = 1 :1 as determined from 1H-NMR spectra),
yield: 56%, Rf value: 0.58 (EtOAc/hexane) = 4:6 (v/v).
Dimethyl 5-ethoxy-1-tosylpyrrolidine-2,2-dicarboxylate (7c). Reaction
time: 5 h, 6e (0.22 g, 1.01 mmol), 2a (0.42 g, 1.52 mmol), colorless solid,
m.p. 118 °C, 0.33 g, yield: 84%, Rf value: 0.48 (EtOAc/hexane) = 4:6 (v/v).
(5b). (trans: cis = 1 :1) 1H-NMR (400 MHz): δ 7.55 (d, J = 8.1 Hz, 2H), 7.50
(d, J = 8.0 Hz, 2H), 7.16 (d, J = 8.6 Hz, 2H), 7.10 (d, J = 7.8 Hz, 2H), 6.89
(d, J = 8.4 Hz, 2H), 6.84 (d, J = 8.5 Hz, 2H), 6.68 (d, J = 8.6 Hz, 2H), 6.65
(d, J = 8.5 Hz, 2H), 4.87 (dd, J = 15.4, 8.0 Hz, 2H), 4.39–4.32 (m, 2H),
4.32–4.27 (m, 1H), 4.19–4.12 (m, 1H), 3.74 (s, 3H), 3.73 (s, 3H), 2.65–
2.56 (m, 1H), 2.48–2.40 (m, 1H), 2.37 (s, 3H), 2.35 (s, 3H), 2.38–2.25 (m,
2H) 1.29 (t, J = 7.2 Hz, 3H), 1.25 (t, J = 7.0 Hz, 3H).. 13C-NMR (100 MHz):
δ 171.9, 171.1, 159.4, 159.3, 143.4, 143.3, 137.4, 137.2, 131.6, 130.9,
129.6, 129.5, 127.6, 127.4, 127.2, 127.2, 114.3, 114.2, 62.2, 62.1, 57.6,
57.5, 55.4, 43.9, 43.2, 21.6, 21.6, 16.4, 13.8, 13.8. IR (neat): 3275, 2956,
2360, 1726, 1514, 1323, 1305, 1247, 1155, 1118, 1062, 829, 812, 750,
705, 665, 580, 559 cm˗1. HRMS (ESI, Q-TOF) m/z: [M + Na]+ Calculated
for C20H23NO5SNa 412.1195, found 412.1165.
(7c). 1H-NMR (400 MHz): δ 7.90 (d, J = 8.2 Hz, 2H), 7.27 (d, J = 8.0 Hz,
2H), 5.34 (d, J = 5.0 Hz, 1H), 3.83 (s, 3H), 3.72 (s, 3H), 3.46–3.38 (m, 1H),
3.33–3.26 (m, 1H), 2.72–2.64 (m, 1H), 2.48 (dd, J = 13.2, 8.2 Hz, 1H), 2.40
(s, 3H), 2.15–2.04 (m, 1H), 1.91 (dd, J = 12.7, 6.8 Hz, 1H), 0.97 (t, J = 6.8
Hz, 3H). 13C-NMR (100 MHz): δ 170.1, 169.4, 143.4, 138.6, 129.1, 128.1,
91.3, 74.4, 62.9, 53.5, 53.1, 35.5, 31. 2, 21.6, 15.0. IR (neat): 2924, 1753,
1737, 1597, 1431, 1342, 1267, 1153, 1097, 1087, 1037, 1022, 991, 935,
856, 775, 740, 675, 590, 543 cm˗1. HRMS (ESI, Q-TOF) m/z: [M + Na]+
calculated for C17H23NO7SNa 408.1093, found 408.1087.
Dimethyl
5-((tert-butyldimethylsilyl)oxy)-1-tosylpyrrolidine-2,2-
dicarboxylate (7d). Reaction time: 8 h, 6f (0.18 g, 0.59 mmol), 2a (0.24 g,
0.89 mmol), light yellow oil, 0.17 g, yield: 62%, Rf value: 0.37
(EtOAc/hexane) = 2:8 (v/v).
Dimethyl
4-(4-methoxyphenyl)-4-methyl-1-tosylazetidine-2,2-
dicarboxylate (5c). Reaction time: 24 h, 4d (0.22 g, 0.79 mmol), 2a (0.32
g, 1.18 mmol), yellow viscous oil, 0.18 g, yield: 52%, Rf value: 0.48
(EtOAc/hexane) = 4:6 (v/v).
(7d). 1H-NMR (400 MHz): δ 7.91 (d, J = 8.3 Hz, 2H), 7.25 (d, J = 8.3 Hz,
2H), 5.63 (d, J = 4.5 Hz, 1H), 3.83 (s, 3H), 3.63 (s, 3H), 2.90–2.82 (m, 1H),
2.50–2.43 (m, 1H), 2.39 (s, 3H), 2.21–2.12 (m, 1H), 1.79 (dd, J = 12.2, 6.4
Hz, 1H), 0.78 (s, 9H), 0.02 (s, 3H), -0.03 (s, 3H). 13C-NMR (100 MHz): δ
170.2, 169.4, 143.1, 139.0, 129.2, 128.1, 127.7, 85.7, 73.8, 53.5, 52.9,
35.0, 34. 6, 25.9, 25.6, 21.6, -4.7, -4.9. IR (neat): 2951, 2854, 2362, 1739,
1597, 1435, 1342, 1257, 1159, 1103, 1029, 1004, 939, 900, 835, 779, 705,
675, 596, 547 cm˗1. HRMS (ESI, Q-TOF) m/z: [M + Na]+ calculated for
C21H33NO7SSiNa 494.1645, found 494.1635.
(5c). 1H-NMR (400 MHz): δ 7.42 (d, J = 9.0 Hz, 2H), 7.23 (d, J = 8.9 Hz,
2H), 7.09 (d, J = 8.2 Hz, 2H), 6.71 (d, J = 8.9 Hz, 2H), 3.93 (s, 3H), 3.78
(s, 3H), 3.70 (s, 3H), 2.86 (d, J = 11.4 Hz, 1H), 2.73 (d, J = 11.7 Hz, 1H),
2.35 (s, 3H), 2.24 (s, 3H). 13C-NMR (100 MHz): δ 169.3, 143.0, 135.3,
128.7, 128.0, 127.9, 127.5, 113.6, 71.7, 55.4, 53.8, 53.0, 43.0, 32.0, 25.8,
21.6. IR (neat): 3354, 3257, 2924, 1739, 1608, 1514, 1436, 1379, 1340,
1294, 1253, 1184, 1155, 1087, 1028, 902, 815, 771, 707, 680, 615, 557
cm˗1. HRMS (ESI, Q-TOF) m/z: [M + Na]+ calculated for C22H25NO7SNa
470.1249, found 470.1242.
Acknowledgments
Dimethyl
7-tosylhexahydropyrano[2,3-b]pyrrole-6,6(2H)-
dicarboxylate (7a). Reaction time: 6 h, 6c (0.15 g, 0.65 mmol), 2a (0.27
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