Sugar-Based Prolinamides in Asymmetric Synthesis
1.79–1.52 (m, 4 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 215.1, (2S,1ЈR)-2-[(Hydroxy)(4-nitrophenyl)methyl]tetrahydropyran-4-one
140.8, 132.4, 129.1, 128.5, 127.9, 123.4, 72.8, 57.7, 42.7, 30.6, 27.8,
24.9 ppm.
(24b): IR (KBr): ν = 3525, 3475, 2930, 2865, 1700, 1613, 1517,
˜
1345, 1130, 1101, 1050, 998, 856 cm–1 1H NMR (500 MHz,
.
CDCl3): δ = 8.27–8.24 (m, 2 H), 7.56–7.52 (m, 2 H), 5.01 (d, J =
8.0 Hz, 1 H), 4.25–4.20 (m, 1 H), 3.79 (dd, J = 3.5, 11.0 Hz, 1 H),
3.76–3.72 (m, 1 H), 3.47 (dd, J = 10.0, 11.5 Hz, 1 H), 2.95–2.88
(m, 1 H), 2.74–2.66 (m, 1 H), 2.55 (td, J = 3.0, 14.5 Hz, 1 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 209.3, 147.8, 147.4, 127.5, 123.9,
71.3, 69.8, 68.9, 57.6, 42.9 ppm.
2-[(4-Bromophenyl)(hydroxy)methyl]cyclohexanone (21h): IR (KBr):
˜
ν = 3512, 2953, 2865, 1689, 1508, 1445, 1387, 1220, 2042, 835 cm–1.
1H NMR (500 MHz, CDCl3): δ = 7.52–7.47 (m, 2 H), 7.25–7.21
(m, 2 H), 4.78 (dd, J = 3.0, 9.0 Hz, 1 H), 4.00 (d, J = 3.0 Hz, 1 H,
OH), 2.61–2.48 (m, 2 H), 2.42–2.34 (m, 1 H), 2.15–2.09 (m, 1 H),
1.86–1.80 (m, 1 H), 1.73–1.52 (m, 3 H), 1.38–1.28 (m, 1 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 215.2, 140.1, 131.5, 128.8, 121.7,
74.2, 57.3, 42.7, 30.7, 27.7, 24.7 ppm.
(2S,1ЈR)-2-[(Hydroxy)(2-nitrophenyl)methyl]tetrahydrothiopyran-4-
one (25a): IR (KBr): ν = 3515, 3487, 2925, 2830, 1718, 1612, 1587,
˜
1510, 1335, 1160, 1129, 1120, 1055, 797 cm–1. 1H NMR (500 MHz,
CDCl3): δ = 8.20–8.16 (m, 2 H), 7.71–7.64 (m, 1 H), 7.56 (t, J =
8.0 Hz, 1 H), 4.97 (d, J = 8.0 Hz, 1 H), 4.25–4.18 (m, 1 H), 3.78–
3.68 (m, 2 H), 3.45 (t, J = 11.5 Hz, 1 H), 2.96–2.89 (m, 2 H), 2.56–
2.49 (m, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 209.8, 148.4,
142.4, 132.8, 128.9, 123.4, 121.7, 71.4, 69.8, 67.9, 57.6, 42.8 ppm.
2-[(4-Fluorophenyl)(hydroxy)methyl]cyclohexanone (21i): IR (KBr):
ν = 3517, 2943, 2860, 1698, 1510, 1449, 1393, 1223, 1120, 1040,
˜
837 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.35–7.27 (m, 2 H),
7.08–7.04 (m, 2 H), 4.80 (dd, J = 1.0, 8.5 Hz, 1 H), 4.01 (d, J =
2.0 Hz, 1 H, OH), 2.63–2.56 (m, 1 H), 2.55–2.45 (m, 1 H), 2.43–
2.34 (m, 1 H), 2.16–2.08 (m, 1 H), 1.92–1.80 (m, 2 H), 1.78–1.64
(m, 1 H), 1.62–1.54 (m, 1 H), 1.36–1.25 (m, 1 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 215.4, 163.3 (d, J = 245.0 Hz), 136.8, 128.7
(d, J = 8.75 Hz), 115.2 (d, J = 21.25 Hz), 74.1, 57.5, 42.6, 30.7,
27.7, 24.6 ppm.
(2S,1ЈR)-2-[(Hydroxy)(4-nitrophenyl)methyl]tetrahydrothiopyran-4-
one (25b): IR (KBr): ν = 3534, 3472, 2928, 2860, 1712, 1615, 1527,
˜
1449, 1355, 1150, 1101, 1050, 856 cm–1. 1H NMR (500 MHz,
CDCl3): δ = 8.22 (d, J = 8.5 Hz, 2 H), 7.53 (d, J = 8.5 Hz, 2 H),
5.05 (dd, J = 8.0, 3.5 Hz, 1 H), 3.66 (s, 1 H, OH), 3.02–2.96 (m, 3
H), 2.85–2.77 (m, 2 H), 2.76–2.63 (m, 1 H), 2.54–2.49 (m, 1 H)
ppm. 13C NMR (125 MHz, CDCl3): δ = 211.2, 147.7, 147.5, 127.6,
123.9, 73.2, 59.4, 44.5, 32.4, 30.7 ppm.
2-[(Hydroxy)(2-methoxyphenyl)methyl]cyclohexanone (21j): IR
(KBr): ν = 3510, 2935, 2858, 1690, 1587, 1441, 1385, 1301, 1126,
˜
751 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.39 (dd, J = 1.5,
7.5 Hz, 1 H), 7.28–7.23 (m, 1 H), 7.01–6.96 (m, 1 H), 6.86 (d, J =
8.0 Hz, 1 H), 5.62 (d, J = 9.0 Hz, 1 H), 3.81 (s, 3 H), 2.78–2.70 (m,
1 H), 2.50–2.43 (m, 1 H), 2.39–2.31 (m, 1 H), 2.09–2.01 (m, 1 H),
1.83–1.75 (m, 1 H), 1.74–1.50 (m, 3 H), 1.48–1.38 (m, 1 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 215.6, 156.7, 129.6, 128.6, 127.8,
120.9, 110.5, 68.6, 57.3, 55.4, 42.6, 30.5, 28.0, 24.7 ppm.
2-[(Hydroxy)(2-nitrophenyl)methyl]cyclopentanone (28a): IR (KBr):
ν = 3527, 3488, 2925, 2845, 1728, 1603, 1550, 1529, 1484, 1345,
˜
1
1119, 1110, 798 cm–1. H NMR (500 MHz, CDCl3): δ = 7.81–7.78
(m, 2 H), 7.72–7.59 (m, 1 H), 7.57–7.38 (m, 1 H), 5.90 [d, J =
3.0 Hz, CHOH (syn)], 4.42 [d, J = 8.5 Hz, CHOH (anti)], 4.50 (s,
1 H), 2.85–2.65 (m, 1 H), 2.60–2.26 (m, 2 H), 2.26–1.95 (m, 2 H),
1.81–1.69 (m, 2 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 219.1,
146.9, 138.6, 133.3, 133.1, 128.9, 128.6, 128.5, 127.9, 124.4, 123.9,
69.0, 66.4, 55.3, 54.7, 38.6, 26.5, 22.8, 20.4, 20.1 ppm.
(2S,1ЈR)-2-[(Hydroxy)(4-methoxyphenyl)methyl]cyclohexanone
(21k): IR (KBr): ν = 3504, 2937, 2862, 1700, 1612, 1513, 1451,
˜
1248, 1176, 1034, 835 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.25–
7.21 (m, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 4.74 (dd, J = 2.5, 9.0 Hz,
1 H), 3.91 (d, J = 3.0 Hz, 1 H, OH), 3.80 (s, 3 H), 2.63–2.49 (m, 1
H), 2.51–2.41 (m, 1 H), 2.40–2.31 (m, 1 H), 2.12–2.05 (m, 1 H),
1.82–1.75 (m, 1 H), 1.72–1.63 (m, 1 H), 1.61–1.50 (m, 2 H), 1.24–
1.19 (m, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 215.7, 159.3,
133.2, 128.2, 113.8, 74.3, 57.5, 55.3, 42.7, 30.8, 27.8, 24.7 ppm.
2-[(Hydroxy)(3-nitrophenyl)methyl]cyclopentanone (28b): IR (KBr):
ν = 3351, 2490, 2873, 1729, 1535, 1349, 1200, 1159, 1043, 809,
˜
727 cm–1. 1H NMR (500 MHz, CDCl3): δ = 8.26–8.22 (m, 1 H),
8.17 (qd, J = 1.0, 8.5 Hz, 0.3 H), 8.15–8.12 (m, 0.7 H), 7.72–7.66
(m, 1 H), 7.56–7.50 (m, 1 H), 5.43 [t, J = 4.0 Hz, 0.7 H (syn)], 4.83
[d, J = 4.5 Hz, 0.3 H (anti)], 4.79 [d, J = 1.0 Hz, 0.3 H, OH (anti)],
2.55–2.44 (m, 1.7 H), 2.43–2.36 (m, 1 H), 2.34–2.25 (m, 0.3 H),
2.21–2.10 (m, 1 H), 2.09–1.96 (m, 2 H), 1.81–1.68 (m, 2 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 214.9, 216.1, 148.4, 145.2, 143.7,
132.7, 131.7, 129.5, 129.3, 123.0, 122.2, 121.6, 120.6, 74.4, 70.2,
56.1, 55.1, 39.0, 38.6, 26.8, 22.4, 20.4 ppm.
(2S,1ЈR)-2-[(Hydroxy)(1-naphthyl)methyl]cyclohexanone (21l): IR
(KBr): ν = 3473, 2932, 2861, 1697, 1510, 1347, 1253, 1128, 1048,
˜
1
803, 750, 698 cm–1. H NMR (500 MHz, CDCl3): δ = 8.28 (d, J =
8.0 Hz, 1 H), 7.92–7.87 (m, 1 H), 7.83 (d, J = 8.5 Hz, 1 H), 7.59
(d, J = 8.0 Hz, 1 H), 7.56–7.48 (m, 3 H), 5.61 (dd, J = 3.0, 8.5 Hz,
1 H), 4.15 (d, J = 3.0 Hz, 1 H, OH), 3.10–2.99 (m, 1 H), 2.58–2.52
(m, 1 H), 2.43 (dt, J = 6.0, 13.5 Hz, 1 H), 2.15–2.08 (m, 1 H),
1.79–1.65 (m, 1 H), 1.55–1.35 (m, 3 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 215.7, 136.9, 134.0, 131.4, 128.9, 128.4, 126.0, 125.5,
125.4, 125.3, 124.0, 72.1, 57.4, 42.8, 31.4, 27.9, 24.9 ppm.
2-[(Hydroxy)(4-nitrophenyl)methyl]cyclopentanone (28c): IR (KBr):
ν = 3442, 2953, 2875, 1725, 1601, 1516, 1346, 1159, 1103, 861 cm–1.
˜
1H NMR (500 MHz, CDCl3): δ = 8.22–8.18 (m, 2 H), 7.56–7.50
(m, 2 H), 5.42 [t, J = 3.5 Hz, 0.8 H (syn)], 4.53 [d, J = 8.5 Hz, 0.2
H (anti)], 4.52 [s, OH (anti)], 2.45 (d, J = 5.0 Hz, 1 H), 2.51–2.45
(m, 1 H), 2.43–2.35 (m, 1 H), 2.07–2.05 (m, 2 H), 1.76–1.67 (m, 2
H) ppm. 13C NMR (125 MHz, CDCl3): δ = 214.7, 213.6, 150.3,
147.2, 127.4, 126.4, 123.7, 123.6, 74.4, 70.4, 56.1, 55.1, 38.9, 38.6,
26.8, 22.4, 20.3 ppm.
(2S,1ЈR)-2-[(Hydroxy)(2-nitrophenyl)methyl]tetrahydropyran-4-one
(24a): IR (KBr): ν = 3520, 3477, 2924, 2835, 1719, 1612, 1516,
˜
1475, 1335, 1129, 1101, 1045, 799 cm–1 1H NMR (500 MHz,
.
CDCl3): δ = 7.92 (dd, J = 1.5, 8.5 Hz, 1 H), 7.81 (dd, J = 1.5,
8.0 Hz, 1 H), 7.67 (dt, J = 1.0, 8.0 Hz, 1 H), 7.49–7.44 (m, 1 H),
5.47 (d, J = 6.5 Hz, 1 H), 4.15 (s, 1 H, OH), 4.24–4.19 (m, 1 H),
2-[(4-Cyanophenyl)(hydroxy)methyl]cyclopentanone (28d): IR (KBr):
ν = 3452, 2963, 2885, 2215, 1728, 1601, 1549, 1519, 1336, 1152,
˜
1
3.92 (ddd, J = 1.5, 6.5, 11.5 Hz, 1 H), 3.84–3.74 (m, 2 H), 3.06 1103, 861 cm–1. H NMR (500 MHz, CDCl3): δ = 7.67–7.62 (m, 2
(dtd, J = 1.0, 6.0, 10.0 Hz, 1 H), 2.71–2.64 (m, 1 H), 2.51 (td, J =
3.5, 14.5 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 209.6,
148.1, 136.1, 133.6, 128.9, 128.8, 124.4, 70.5, 68.4, 67.4, 57.9,
43.3 ppm.
H), 7.49–7.44 (m, 2 H), 5.37 [t, J = 3.5 Hz, 0.75 H (syn)], 4.78 [d,
J = 9.5 Hz, 0.25 H (anti)], 4.70 [d, J = 1.0 Hz, 0.25 H, OH (anti)],
2.51–2.22 (m, 3 H), 2.19–2.10 (m, 1 H), 2.08–1.88 (m, 2 H), 1.80–
1.65 (m, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 215.5, 214.3,
Eur. J. Org. Chem. 2012, 6390–6406
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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