C.-K. Pei, M. Shi / Tetrahedron: Asymmetry 22 (2011) 1239–1248
1247
4.7.15. Isopropyl 6-bromo-2-methyl-4-((4-methylphenylsulfon-
amido)methyl)-4H-chromene-3-carboxylate 3cd
white solid (36.1 mg, 72%); mp 155–157 °C; 1H NMR
(400 MHz, CDCl3, TMS) 1.26 (d, J = 6.4 Hz, 3H), 1.29 (d,
4.7.19. Isopropyl 6-methoxy-2-methyl-4-((4-methylphenyl-
sulfonamido)methyl)-4H-chromene-3-carboxylate 3gd
A
A
white solid (34.1 mg, 75%); mp 157–159 °C; 1H NMR
d
(300 MHz, CDCl3, TMS) d 1.25 (d, J = 6.0 Hz, 3H), 1.27 (d,
J = 6.4 Hz, 3H), 2.39 (s, 3H), 2.40 (s, 3H), 5.02 (sept, J = 6.4 Hz,
1H), 5.34 (br s, 1H), 5.44 (d, J = 6.0 Hz, 1H), 6.89 (d, J = 8.8 Hz,
1H), 7.11 (d, J = 1.6 Hz, 1H), 7.17 (d, J = 7.6 Hz, 2H), 7.25 (d,
J = 8.8 Hz, 1H), 7.46 (d, J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d 19.8, 21.5, 21.8, 21.9, 47.7, 68.6, 103.3, 116.6, 118.0, 121.1,
126.6, 129.3, 131.9, 132.1, 138.9, 143.0, 149.8, 162.9, 165.8; IR
J = 6.0 Hz, 3H), 2.37 (s, 3H), 2.37 (s, 3H), 3.61 (s, 3H), 5.01 (sept,
J = 6.0 Hz, 1H), 5.09 (d, J = 6.0 Hz, 1H), 5.54 (d, J = 6.0 Hz, 1H),
6.65 (d, J = 3.0 Hz, 1H), 6.77 (dd, J = 3.0 Hz, 9.0 Hz, 1H), 6.96 (d,
J = 9.0 Hz, 1H), 7.16 (d, J = 7.8 Hz, 2H), 7.49 (d, J = 7.8 Hz, 2H); 13C
NMR (100 MHz, CDCl3) d 19.9, 21.3, 21.8, 21.9, 48.6, 55.3, 68.3,
102.4, 112.0, 116.4, 117.2, 119.9, 126.7, 129.0, 139.4, 142.6,
(neat)
m
3672, 2972, 2901, 1709, 1652, 1633, 1602, 1376, 1328,
144.9, 156.1, 163.1, 166.2; IR (neat)
m 3288, 2924, 2877, 1658,
1234, 1066, 907, 777 cmꢁ1; MS (ESI) m/e 502 (M+Na); HRMS
1494, 1374, 1340, 1289, 1224, 1204, 1155, 1073, 811, 762 cmꢁ1
;
(ESI) for C21H22BrNNaO5S (M+Na): 502.0294; found: 502.0309.
MS (ESI) m/e 454 (M+Na); HRMS (ESI) for C22H25NO6SNa (M+Na):
½
a 2D0
ꢂ
¼ þ20:8 (c 0.35, CHCl3) (76% ee); Chiralcel OD-H, hex-
454.1295; found: 454.1311. ½a D20
¼ þ17:4 (c 0.50, CHCl3) (64%
ꢂ
ane/iPrOH = 80:20,
0.7 mL/min,
214 nm,
tmajor = 8.58 min,
ee); Chiralcel OD-H, hexane/iPrOH = 95:5, 0.7 mL/min, 214 nm,
tminor = 10.33 min.
tmajor = 30.49 min, tminor = 38.12 min.
4.7.20. Isopropyl 2,8-dimethyl-4-(4-methylphenylsulfon-
4.7.16. Isopropyl 6,8-dichloro-2-methyl-4-(4-methylphenyl-
amido)-4H-chromene-3-carboxylate 3kd
sulfonamido)-4H-chromene-3-carboxylate 3dd
white solid (35.0 mg, 80%); mp 124–126 °C; 1H NMR
A
yellow solid (13.3 mg, 27%); mp 145–147 °C; 1H NMR
A
(300 MHz, CDCl3, TMS)
d 1.24 (d, J = 6.6 Hz, 3H), 1.26 (d,
(400 MHz, CDCl3, TMS)
d 1.26 (d, J = 6.4 Hz, 3H), 1.29 (d,
J = 6.6 Hz, 3H), 2.30 (s, 3H), 2.38 (s, 3H), 2.39 (s, 3H), 4.95–5.02
(m, 2H), 5.58 (d, J = 4.5 Hz, 1H), 6.87 (t, J = 7.5 Hz, 1H), 7.05–7.10
(m, 2H), 7.16 (d, J = 7.8 Hz, 2H), 7.52 (d, J = 7.8 Hz, 2H); 13C NMR
(75 MHz, CDCl3) d 15.6, 19.9, 21.5, 21.9, 22.0, 48.4, 68.4, 103.5,
119.6, 124.1, 125.5, 126.9, 127.1, 129.2, 130.3, 139.3, 142.7,
J = 6.4 Hz, 3H), 2.40 (s, 3H), 2.44 (s, 3H), 5.03 (sept, J = 6.4 Hz,
1H), 5.13 (d, J = 6.0 Hz, 1H), 5.47 (d, J = 6.0 Hz, 1H), 6.99 (d,
J = 2.4 Hz, 1H), 7.20 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 2.4 Hz, 1H),
7.50 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 19.6, 21.4,
21.8, 21.9, 47.8, 68.9, 103.8, 122.1, 122.3, 126.8, 127.7, 129.0,
149.2, 163.0, 166.1; IR (neat)
m 3312, 2954, 2919, 1689, 1648,
129.3, 129.4, 138.8, 143.2, 145.6, 162.7, 165.4; IR (neat)
m 3005,
1593, 1531, 1465, 1382, 1283, 1242, 1089, 763, 660 cmꢁ1; MS
2926, 1683, 1580, 1364, 1275, 1257, 1158, 980, 750, 658 cmꢁ1
;
(ESI) m/e 438 (M+Na); HRMS (ESI) for C22H25NNaO5S (M+Na):
MS (ESI) m/e 492 (M+Na); HRMS (ESI) for C21H21NO5SCl2Na
438.1346; found: 438.1349. ½a D20
¼ þ11:0 (c 0.30, CHCl3) (87%
ꢂ
(M+Na): 492.0410; found: 492.0427. ½a D20
¼ þ9:6 (c 0.50, CHCl3)
ꢂ
ee); Chiralcel IC, hexane/iPrOH = 80:20, 1.0 mL/min, 220 nm,
(38% ee); Chiralcel IC, hexane/iPrOH = 70:30, 0.5 mL/min, 214 nm,
tmajor = 22.28 min, tminor = 33.38 min.
tmajor = 19.21 min, tminor = 25.54 min.
4.7.21. Isopropyl 6,8-di-tert-butyl-2-methyl-4-(4-methyl-
phenylsulfonamido)-4H-chromene-3-carboxylate 3ld
4.7.17. Isopropyl 6,8-dibromo-2-methyl-4-(4-methylphenyl-
sulfonamido)-4H-chromene-3-carboxylate 3ed
A
white solid (34.8 mg, 65%); mp 128–130 °C; 1H NMR
A
white solid (12.2 mg, 21%); mp 155–157 °C; 1H NMR
(400 MHz, CDCl3, TMS) d 1.18 (s, 9H), 1.28 (d, J = 6.0 Hz, 3H), 1.30
(d, J = 6.0 Hz, 3H), 1.42 (s, 9H), 2.35 (s, 3H), 2.45 (s, 3H), 4.85 (d,
J = 6.4 Hz, 1H), 5.06 (sept, J = 6.0 Hz, 1H), 5.58 (d, J = 6.4 Hz, 1H),
7.06 (d, J = 2.4 Hz, 1H), 7.13 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 2.4 Hz,
1H), 7.51 (d, J = 8.0 Hz, 2H); 13C NMR (75 MHz, CDCl3) d 14.2,
19.7, 21.4, 21.8, 22.0, 30.0, 31.2, 34.4, 34.9, 48.9, 68.3, 103.7,
119.5, 123.6, 124.0, 126.7, 129.1, 136.5, 139.4, 142.5, 146.7,
(300 MHz, CDCl3, TMS)
d 1.27 (d, J = 6.0 Hz, 3H), 1.29 (d,
J = 6.0 Hz, 3H), 2.41 (s, 3H), 2.45 (s, 3H), 5.02–5.10 (m, 2H), 5.47
(d, J = 6.0 Hz, 1H), 7.14 (d, J = 2.1 Hz, 1H), 7.20 (d, J = 8.1 Hz, 2H),
7.48 (d, J = 8.1 Hz, 2H), 7.54 (d, J = 2.1 Hz, 1H); 13C NMR
(100 MHz, CDCl3) d 19.6, 21.5, 21.78, 21.85, 47.8, 68.9, 104.0,
111.1, 116.5, 122.4, 126.7, 129.3, 131.3, 134.9, 138.7, 143.2,
147.0, 162.8, 165.3; IR (neat)
m 3290, 3005, 1682, 1571, 1459,
162.9, 166.0; IR (neat)
m 3277, 2931, 2962, 2926, 1708, 1664,
1365, 1275, 1258, 1203, 1157, 1073, 1026, 979, 749, 657 cmꢁ1
;
1640, 1589, 1460, 1364, 1240, 1201, 1159, 1070, 760, 739,
MS (ESI) m/e 579 (M+Na); HRMS (ESI) for C21H21NNaBr2O5S
663 cmꢁ1; MS (ESI) m/e 536 (M+Na); HRMS (ESI) for C29H39NNaO5S
(M+Na): 579.9399; found: 579.9425. ½a D20
¼ þ6:4 (c 0.35, CHCl3)
ꢂ
(M+Na): 536.2441; found: 536.2461. ½a D20
¼ þ50:6 (c 0.35, CHCl3)
ꢂ
(21% ee); Chiralcel IC, hexane/iPrOH = 80:20, 0.7 mL/min, 214 nm,
(72% ee); Chiralcel AD-H, hexane/iPrOH = 90:10, 0.8 mL/min,
tmajor = 19.83 min, tminor = 28.38 min.
230 nm, tmajor = 6.18 min, tminor = 14.73 min.
4.7.18. Isopropyl 8-methoxy-2-methyl-4-(4-methylphenyl-
4.7.22. Isopropyl 2-methyl-4-(4-nitrophenylsulfonamido)-4H-
sulfonamido)-4H-chromene-3-carboxylate 3fd
chromene-3-carboxylate 3hd
white solid (35.9 mg, 79%); mp 157–159 °C; 1H NMR
A
white solid (29.8 mg, 69%); mp 152–155 °C; 1H NMR
A
(400 MHz, CDCl3, TMS)
d 1.24 (d, J = 6.0 Hz, 3H), 1.28 (d,
(400 MHz, CDCl3, TMS)
d 1.23 (d, J = 6.0 Hz, 3H), 1.28 (d,
J = 6.0 Hz, 3H), 2.21 (s, 3H), 2.38 (s, 3H), 3.81 (s, 3H), 4.98 (sept,
J = 6.0 Hz, 1H), 5.27 (d, J = 7.2 Hz, 1H), 5.65 (d, J = 7.2 Hz, 1H),
6.79 (d, J = 7.6 Hz, 1H), 6.89–6.96 (m, 2H), 7.18 (d, J = 8.0 Hz, 2H),
7.60 (d, J = 8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) d 19.4, 21.4,
21.7, 21.8, 47.7, 55.9, 68.4, 103.4, 110.8, 120.8, 121.3, 124.3,
J = 6.0 Hz, 3H), 2.42 (s, 3H), 5.00 (sept, J = 6.0 Hz, 1H), 5.32 (d,
J = 4.2 Hz, 1H), 5.61 (d, J = 4.2 Hz, 1H), 6.93 (t, J = 8.4 Hz, 1H), 7.07
(d, J = 8.4 Hz, 1H), 7.21–7.26 (m, 2H), 7.75 (d, J = 8.8 Hz, 2H), 8.18
(d, J = 8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 20.1, 21.9, 48.7,
68.7, 103.2, 116.5, 118.9, 123.7, 124.7, 128.1, 129.50, 129.52,
126.8, 129.1, 139.2, 140.3, 142.6, 147.2, 162.5, 165.9; IR (neat)
m
147.7, 149.5, 150.8, 163.4, 166.0; IR (neat)
m 3279, 2988, 1657,
3298, 2921, 1704, 1589, 1332, 1276, 1210, 1156, 1092, 1015,
1527, 1373, 1341, 1277, 1240, 1199, 1154, 1087, 1015, 764,
764, 748, 660 cmꢁ1; MS (ESI) m/e 454 (M+Na); HRMS (ESI) for
748 cmꢁ1
;
MS (ESI) m/e 455 (M+Na); HRMS (ESI) for
C22H25NNaO6S (M+Na): 454.1295; found: 454.1314. ½a D20
¼ þ22:0
ꢂ
C
20H20N2NaO7S (M+Na): 455.0883; found: 455.0890. ½a D20
¼ ꢁ3:0
ꢂ
(c 0.20, CHCl3) (76% ee); Chiralcel OJ-H, hexane/iPrOH = 80:20,
0.7 mL/min, 214 nm, tmajor = 20.09 min, tminor = 29.13 min.
(c 0.30, CHCl3) (65% ee); Chiralcel AD-H, hexane/iPrOH = 70:30,
0.6 mL/min, 214 nm, tmajor = 31.21 min, tminor = 52.54 min.