Asymmetric Aza-Morita–Baylis–Hillman-Type Reactions
7.2 Hz, 1H), 6.12 (bd, J=10.5 Hz, 1H), 5.85 (bd, J=
11.4 Hz, 1H), 2.47–2.75 (m, 2H), 1.45 (s, 9H), 1.20 (t, J=
7.2 Hz, 3H); 13C NMR (300 MHz, CDCl3, 258C): d=195.3,
159.3, 155.6, 142.6, 141.1, 134.7, 130.0, 127.6, 126.4, 124.3,
80.1, 50.2, 28.6, 23.0, 13.2; [a]D: +129.7 (c 0.24, CHCl3);
HR-MS (ESI): m/z=346.1176, calcd. for [M+Na]+
(C17H22ClNO3): 346.1186. The enantiomeric excess (99%)
was determined by HPLC (IC column, n-heptane:i-PrOH=
90:10, l=230 nm, 1.0 mLminÀ1): tR =major enantiomer
9.4 min, minor enantiomer 17.6 min.
2.44–2.69 (m, 2H), 1.45 (s, 9H), 1.18 (t, J=7.5 Hz, 3H);
13C NMR (300 MHz, CDCl3, 258C): d=194.9, 158.6, 155.2,
144.5, 140.5, 126.9, 124.6, 124.1, 79.9, 47.2, 28.4, 22.5, 13.0;
[a]D: +50.0 (c 0.45, CHCl3); HR-MS (ESI): m/z=318.1130,
calcd. for [M+Na]+ (C15H21NO3S): 318.1134. The enantio-
meric excess (99%) was determined by HPLC (IC column,
n-heptane:i-PrOH=98:2, l=210 nm, 1.0 mLminÀ1): tR =
major enantiomer 62.7 min, minor enantiomer 73.3 min.
(R)-tert-Butyl
(E)-1-(4-fluorophenyl)-2-formylpent-2-
enylcarbamate (4o): Colorless oil; yield: 74%. IR (KBr): n=
(R)-tert-Butyl (E)-2-formyl-1-(4-nitrophenyl)pent-2-enyl-
carbamate (4j): Yellow solid; yield: 50%; IR (KBr): n=
3433, 2975, 2937, 2875, 1712, 1680, 1518, 1491, 1346, 1235,
3429, 2983, 2915, 2864, 1713, 1682, 1493, 1371, 1231, 1160,
1
1017, 907 cmÀ1; H NMR (300 MHz, CDCl3, 258C): d=9.37
(d, J=1.5 Hz, 1H), 6.98 (t, J=8.7 Hz, 2H), 6.66 (t, J=
7.2 Hz, 1H), 6.13 (bd, J=9.6 Hz, 1H), 5.85 (bd, J=9 Hz,
1H), 2.45–2.73 (m, 2H), 1.45 (s, 9H), 1.19 (t, J=7.5 Hz,
3H); 13C NMR (300 MHz, CDCl3, 258C): d=195.2, 163.5,
160.3, 155.4, 141.2, 136.0, 127.7, 115.3, 79.7, 49.9, 28.4, 22.6,
12.9; [a]D: +78.5 (c 1.0, CHCl3); HR-MS (ESI): m/z=
330.1476, calcd. for [M+Na]+ (C17H22FNO3): 330.1481,
founded. The enantiomeric excess (95%) was determined by
HPLC (IA column, n-heptane:i-PrOH=98:2, l=254 nm,
1.0 mLminÀ1): tR =major enantiomer 10.5 min, minor enan-
tiomer 11.4 min.
1
1166, 1049, 911, 851, 700 cmÀ1; H NMR (300 MHz, CDCl3,
258C): d=9.35 (d, J=1.2 Hz, 1H), 8.15 (d, J=9 Hz, 2H),
7.42 (d, J=8.4 Hz, 2H), 6.75 (t, J=7.5 Hz, 1H), 6.11 (bd,
J=11.6 Hz, 1H), 5.96 (bd, J=9.9 Hz, 1H), 2.48–2.77 (m,
2H), 1.45 (s, 9H), 1.22 (t, J=7.5 Hz, 3H); 13C NMR
(300 MHz, CDCl3, 258C): d=194.9, 159.5, 155.4, 147.8,
147.1, 140.6, 126.8, 123.8, 80.3, 50.0, 28.4, 22.9, 13.0; [a]D:
+172.0 (c 0.29, CHCl3); HR-MS (ESI): m/z=357.1426,
calcd. for [M+Na]+ (C17H22N2O5): 357.1421. The enantio-
meric excess (97%) was determined by HPLC (IC column,
n-heptane:i-PrOH=92:8, l=230 nm, 1.0 mLminÀ1): tR =
major enantiomer 38.0 min, minor enantiomer 78.8 min.
(R)-tert-Butyl 2-formyl-1-phenylallylcarbamate (4p): Pale
yellow oil; yield: 26%; IR (KBr): n=3345, 3318, 2978, 2931,
(R)-tert-Butyl
(E)-1-(4-bromophenyl)-2-formylpent-2-
1712, 1697, 1496, 1367, 1249, 1166, 1048, 755, 700 cmÀ1
;
enylcarbamate (4k): Colorless oil; yield: 54%; IR (KBr): n=
1H NMR (300 MHz, CDCl3, 258C): d=9.56 (s, 1H), 7.22–
7.34 (m, 5H), 6.52 (s, 1H), 6.20 (s, 1H), 5.65 (bd, J=8.1 Hz,
1H), 5.43 (bd, J=9.6 Hz, 1H), 1.44 (s, 1H); 13C NMR
(300 MHz, CDCl3, 258C): d=193.2, 154.9, 149.1, 139.3,
134.8, 128.7, 127.7, 126.7, 80.0, 54.5,28.3; [a]D: À13.5 (c 0.26,
CHCl3); HR-MS (ESI): m/z=284.1257, calcd. for [M+Na]+
(C15H19NO3): 284.1263. The enantiomeric excess (82%) was
determined by HPLC (IA column n-heptane:i-PrOH=98:2,
l=210 nm, 1.0 mLminÀ1): tR =major enantiomer 22.4 min,
minor enantiomer 20.8 min.
3432, 2976, 2933, 2875, 1712, 1685, 1487, 1367, 1235, 1165,
1
1010, 904 cmÀ1; H NMR (300 MHz, CDCl3, 258C): d=9.35
(d, J=1.5 Hz, 1H), 7.41 (d, J=8.7 Hz, 2H), 6.66 (t, J=
7.5 Hz, 1H), 6.12 (bd, J=9.6 Hz, 1H), 5.83 (bd, J=9 Hz,
1H), 2.43–2.73 (m, 2H), 1.44 (s, 9H), 1.18 (t, J=7.5 Hz,
3H); 13C NMR (300 MHz, CDCl3, 258C): d=195.2, 159.0,
155.4, 141.0, 139.4, 131.6, 127.8, 121.1, 79.9, 50.0, 28.4, 22.7,
13.0; [a]D :+88.7 (c 0.4, CHCl3); HR-MS (ESI): m/z=
390.072, calcd. for [M+Na]+ (C17H22N2O5): 357.1421. The
enantiomeric excess (99%) was determined by HPLC (IC
(R)-Benzyl (E)-2-formyl-1-phenylpent-2-enylcarbamate
(4q): Colorless oil; yield: 69%; IR (KBr): n=3428, 2969,
column,
n-heptane:i-PrOH=90:10,
l=230 nm,
1.0 mLminÀ1): tR =major enantiomer 12.7 min, minor enan-
tiomer 21.2 min.
2935, 2875, 1720, 1679, 1498, 1327, 1226, 1043, 741, 698 cmÀ1
;
1H NMR (300 MHz, CDCl3, 258C): d=9.37 (d, J=1.5 Hz,
1H), 7.36–7.24 (m, 10H), 6.68 (t, J=12 Hz, 1H), 6.46 (bd,
J=12 Hz, 1H), 5.96 (bd, J=9.3 Hz, 1H), 5.13 (d, J=3.3 Hz,
2H), 2.74–2.46 (m, 2H), 1.19 (t, J=7.5 Hz, 3H); 13C NMR
(300 MHz, CDCl3, 258C): d=195.4, 159.2, 156.3, 141.1,
139.9, 136.6, 128.7, 128.7, 128.3, 128.2, 127.5, 126.2, 67.1,
51.3, 22.8, 13.1 ppm; [a]D: +65.8 (c 0.4, CHCl3); HR-MS
(ESI): m/z=346.1408, calcd. for [M+Na]+ (C20H21NO3):
346.1414. The enantiomeric excess (99%) was determined
by HPLC (IA column, n-heptane:i-PrOH=80:20, l=
230 nm, 1.0 mLminÀ1): tR =major enantiomer 9.2 min, minor
enantiomer 8.0 min.
(R)-tert-Butyl (E)-2-formyl-1-(furan-2-yl)pent-2-enylcar-
bamate (4l): Brown oil; yield: 48%; IR (KBr): n=3436,
2974, 2933, 2875, 1712, 1683, 1491, 1365, 1236, 1166, 1011,
1
738 cmÀ1; H NMR (300 MHz, CDCl3, 258C): d=9.38 (d, J=
1.5 Hz, 1H), 7.28 (d, J=2.4 Hz, 1H), 6.64 (t, J=7.1 Hz,
1H), 6.28 (dd, J=1.8, 3.3 Hz, 1H), 6.13 (d, J=3 Hz, 1H),
6.09 (bd, J=9 Hz, 1H), 5.90 (bd, J=10.5 Hz, 1H), 2.46–2.66
(m, 2H), 1.44 (s, 9H), 1.17 (t, J=7.5 Hz, 3H); 13C NMR
(300 MHz, CDCl3, 258C): d=194.9, 159.4, 155.4, 153.1,
142.0, 139.4, 110.6, 106.2, 80.0, 45.8, 28.6, 22.7, 13.1; [a]D:
+48.1 (c 0.27, CHCl3); HR-MS (ESI): m/z=302.1362, calcd.
for [M+Na]+ (C15H21NO4): 302.1368. The enantiomeric
excess (99%) was determined by HPLC (IC column, n-hep-
tane:i-PrOH=98:2, l=230 nm, 1.0 mLminÀ1): tR =major
enantiomer 62.6 min, minor enantiomer 133.3 min.
(R)-Benzyl (E)-2-formyl-1-phenylhept-2-enylcarbamate
(4r): White solid; yield: 70%; IR (KBr): n=3320, 2957,
1
2931, 2869, 1683, 1520, 1234, 1041, 745, 696 cmÀ1; H NMR
(300 MHz, CDCl3, 258C): d=9.37 (d, J=1.5 Hz, 1H), 7,23–
7,37 (m, 10H), 6.69 (t, J=7.5 Hz, 1H), 6.46 (bd, J=9.9 Hz,
1H), 5.96 (bd, J=9.9 Hz, 1H), 5.12 (s, 2H), 2.44–2.71 (m,
2H), 1.32–1.62 (m, 4H), 0.94 (t, J=7.2 Hz, 3H); 13C NMR
(300 MHz, CDCl3, 258C): d=195.3, 157.9, 156.1, 141.4,
139.8, 136.4, 128.6, 128.5, 128.1, 128.0, 127.3, 126.0, 66.9,
51.2, 30.6, 29.0, 22.5, 13.8; [a]D: +60.0 (c 1.03, CHCl3); HR-
MS (ESI): m/z=374.1727, calcd. for [M+Na]+ (C22H25NO3):
(R)-tert-Butyl (E)-2-formyl-1-(thiophen-2-yl)pent-2-enyl-
carbamate (4m): Brown oil; yield: 74%; IR (KBr): n=3431,
2975, 2933, 2875, 1710, 1681, 1489, 1367, 1230, 1164, 1048,
1
701 cmÀ1; H NMR (300 MHz, CDCl3, 258C): d=9.40 (d, J=
1.5 Hz, 1H), 7.16 (d, J=3.6 Hz, 1H), 6.90 (dd, J=1.2 Hz,
3.6 Hz, 1H), 6.82 (d, J=3.3 Hz, 1H), 6.41 (t, J=7.2 Hz,
1H), 6.24 (bd, J=8.5 Hz, 1H), 6.07 (bd, J=10 Hz, 1H),
Adv. Synth. Catal. 2011, 353, 1096 – 1108
ꢃ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1105