Molecules 2015, 20, 22028–22043
hexane/AcOEt (90:10), afforded the diastereoisomers (R,S)-10a (30 mg, 26%) and (S,S)-10a (31 mg,
27%), both as an amber liquid.
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(R,S)-10a: rαsD + 87.13 (c 0.95, CHCl3). IR (cm´1): 2933, 1734, 1685, 1604, 1482, 1190, 760, 698.
1H-NMR (CDCl3, 400 MHz) δ: 1.57 (d, J = 7.2 Hz, 3H), 2.76 (dd, J = 17.6, 10.4 Hz, 1H), 2.84 (dd,
J = 17.6, 8.4 Hz, 1H), 3.38 (dddd, J = 10.4, 8.8, 8.4, 8.4 Hz, 1H), 3.79 (dd, J = 12.0, 8.8 Hz, 1H), 3.91
(s, 3H), 4.19 (dd, J = 12.0, 8.4 Hz, 1H), 5.25 (q, J = 7.2 Hz, 1H), 7.11–7.20 (m, 4H), 7.25–7.29 (m, 1H),
7.29–7.36 (m, 2H), 7.48–7.51 (m 1H), 7.70–7.75 (m, 3H). 13C-NMR (CDCl3, 100 MHz) δ: 19.4, 35.8, 41.1,
44.7, 52.5, 55.3, 105.6, 118.9, 126.6, 126.7, 127.0, 127.1, 127.4, 129.0, 129.4, 133.7, 136.2, 140.3, 157.6, 173.4,
175.4. MS (CI+): m/z 374 (100%), 373 (38%) 212 (70%), 185 (23%), 162 (18%). HRMS (CI) calculated for
C24H24NO3 [M + H]+, m/z 374.1756; found for [M + H]+, m/z 374.1772.
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(S,S)-10a: rαsD + 83.53 (c 0.82, CHCl3). IR (cm´1): 2933, 1734, 1686, 1604, 1482, 1189, 760, 698.
1H-NMR (CDCl3, 400 MHz) δ: 1.55 (d, J = 6.8 Hz, 3H), 2.57 (dd, J = 17.6, 8.0 Hz, 1H), 2.91 (dd,
J = 17.6, 8.8 Hz, 1H), 3.45–3.49 (m, 1H), 3.67 (dd, J = 11.6, 6.8 Hz, 1H), 3.90 (s, 3H), 4.30 (dd, J = 11.6,
8.0 Hz, 1H), 5.22 (q, J = 6.8 Hz, 1H), 6.91–6.93 (m, 2H), 7.05–7.14 (m, 5H), 7.45–7.46 (m, 1H), 7.67–7.68
(m, 3H). 13C-NMR (CDCl3, 100 MHz) δ: 19.5, 36.2, 41.4, 44.9, 52.8, 55.5, 105.8, 119.0, 126.5, 126.6, 127.2,
127.4, 127.4, 129.0, 129.1, 129.6, 133.9, 136.2, 141.2, 157.8, 173.8, 175.6. MS (CI+): m/z 374 (70%), 373
(55%) 212 (100%), 185 (32%), 184 (19%), 162 (18%), 141 (<10%). HRMS (CI) calculated for C24H24NO3
[M + H]+, m/z 374.1756; found for [M + H]+, m/z 374.1772.
3.8.2. (R)-4-(4-Chlorophenyl)-1-((S)-2-(6-methoxynaphth-2-yl)propionyl)-pyrrolidin-2-one (R,S)-10b
and (S)-4-(4-Chlorophenyl)-1-((S)-2-(6-methoxynaphth-2-yl)propionyl)-pyrrolidin-2-one (S,S)-10b
According to the general procedure, 8b (86 mg, 0.4 mmol) with LDA (56 mg, 0.52 mmol) and
(S)-9 (27 mg, 1.1 mmol), followed by purification in column chromatography using hexane/AcOEt
(85:15), afforded the diastereoisomers (R,S)-10b (86 mg, 49%) and (S,S)-10b (92 mg, 51%), both as an
colorless liquid.
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(R,S)-10b: rαsD + 44.48 (c 1.0, CHCl3). IR (cm´1): 2929, 1735, 1686, 810. H-NMR (CDCl3, 400 MHz)
δ: 1.54 (d, J = 7.2 Hz, 3H), 2.69 (dd, J = 17.2, 10.0 Hz, 1H), 2.82 (dd, J = 17.2, 8.4 Hz, 1H), 3.35 (dddd,
J = 10.0, 8.8, 8.4, 8.4 Hz, 1H), 3.74 (dd, J = 12.0, 8.8 Hz, 1H), 3.90 (s, 3H), 4.17 (dd, J = 12.0, 8.4 Hz,
1H) 5.21 (q, J = 7.2 Hz, 1H), 7.10–7.14 (m, 4H), 7.29–7.31 (m, 2H), 7.45–7.48 (m, 1H), 7.68–7.71 (m, 3H).
13C-NMR (CDCl3, 100 MHz) δ: 19.5, 35.5, 41.2, 44.9, 52.5, 55.5, 105.7, 119.1, 126.8, 127.2, 127.3, 128.2,
129.1 129.3, 129.5, 133.4, 133.8, 136.2, 138.9, 157.8, 173.2, 175.6. MS (FAB+): m/z 408 (25%), 185 (100%),
136 (24%), 95 (28%), 69 (55%), 55 (30%). HRMS (FAB) calculated for C24H23ClNO3 [M + H]+, m/z
408.1366; found for [M + H]+, m/z 408.1383.
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(S,S)-10b: rαsD + 39.08 (c 0.97, CHCl3). IR (cm´1): 2932, 1735, 1688, 811. H-NMR (CDCl3, 200 MHz)
δ: 1.55 (d, J = 7.2 Hz, 3H), 2.50 (dd, J = 17.2, 7.2 Hz, 1H), 2.90 (dd, J = 17.2, 8.4 Hz, 1H), 3.42 (m,
1H), 3.62 (dd, J = 11.6, 6.0 Hz, 1H), 3.92 (s, 3H), 4.25 (dd, J = 11.6, 8.0 Hz, 1H), 5.20 (q, 7.2 Hz,
1H), 6.76–6.78 (m, 2H), 6.92–6.95 (m, 2H), 7.12–7.15 (m, 2H), 7.41–7.44 (m, 1H), 7.66–7.69 (m, 3H).
13C-NMR (CDCl3, 100 MHz) δ: 19.3, 35.6, 41.2, 45.0, 52.7, 55.5, 105.7, 119.1, 126.6, 127.2, 127.8, 129.1,
129.6, 133.1, 133.9, 136.0, 139.9, 157.9, 173.4, 175.6. MS (FAB+): m/z 408 (12%), 407 (<10%), 307 (27%),
289 (13%), 212 (18%), 185 (12%), 154 (100%), 136 (66%), 107 (18%), 77 (13%). HRMS (FAB) calculated
for C24H23ClNO3 [M + H]+, m/z 408.1366; found for [M + H]+, m/z 408.1383.
3.8.3. (R)-1-((S)-2-(6-Methoxynaphth-2-yl)propionyl-4-(4-methylphenyl)-pyrrolidin-2-one (R,S)-10c
and (S)-1-((S)-2-(6-Methoxynaphth-2-yl)propionyl-4-(4-methylphenyl)-pyrrolidin-2-one (S,S)-10c,
(R,S)-10c and (S,S)-10c
According to the general procedure, the reaction of 8c (0.2 g, 1.14 mmol) with LDA (0.14 g, 1.37
mmol) and (S)-9 (0.709 g, 2.85 mmol), followed by purification in column chromatography using
hexane/AcOEt (90:10), afforded the diastereoisomers (R,S)-10c (0.21 g, 49%) as a colorless liquid, and
˝
(S,S)-10c (0.19 g, 44%) as a beige solid, m.p.: 61–64 C.
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