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General procedure
for allylation: Indium metal (0.506 mg, 4.4 mmol) and allyl
bromide (970 mg, 0.75 ml, 8 mmol) were added to a stirred solution
of aldehydes 1a-c (4
mmol) in 20 mL 50% aq THF. The reaction was allowed to
proceed till the aldehyde was consumed (12-16 h) (TLC).
Finally, a saturated aqueous solution of NH4Cl was added
and the solution was extracted with CH2Cl2.
The combined organic layers were dried and concentrated to give 2a-c,
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Physical and spectral data for the
representative cases are given here. (RS)-2a: Yellow liquid (76%); IR (Neat):
3410, 2980, 1620 cm-1; MS (m/z): 210 (M+); 1H
NMR (CDCl3): δ 2.32-2.64 (m, 2 H, CH2),
3.33 (s, 3 H, CH3), 3.42 (s, 3 H, CH3), 4.62
(dd, 1 H, J = 5.1 and 7.2 Hz,
CH), 5.10-5.18 (m, 2 H, CH2), 5.76-5.90
(m, 1 H, CH), 7.21 (m, 1 H, Ur-6H);13C NMR
(CDCl3): δ 27.71 (CH3), 37.03 (CH3),
40.78 (CH2), 67.49 (CH), 114.67 (Ur-C5), 118.55 (CH2),
134.10 (CH), 139.35 (Ur-C6), 151.38 (C=O), 162.87 (C=O).
(RS)-2b: Pale
yellow liquid (80%); IR (Neat): 3447, 2958, 1560
cm-1;
MS (m/z): 210 (M+); 1H
NMR (CDCl3): δ 2.39-2.66 (m, 3 H, CH2 and
OH), 3.98 (s, 3 H, OCH3), 4.01 (s, 3 H, OCH3),
4.83 (dd, 1 H, J = 7.6 and 5.1
Hz, CH), 5.12-5.19 (m, 2 H, CH2), 5.74-5.82
(m, 1 H, CH), 8.24 (s, 1 H, Pym-6H); 13C
NMR/DEPT (CDCl3): δ 41.15 (-ve,
CH2), 53.82 (+ve, OCH3), 54.61 (+ve,
OCH3), 66.67 ((+ve, CH), 118.28 (-ve, =CH2),
133.73 (+ve, =CH), 144.78 (ab, Pym-C5), 155.70 (+ve,
Pym-C6), 164.42 (ab, Pym-C), 168.03 (ab, Pym-C). (R)-3a: Pale
liquid; [α]D
27: +66.53
(c 0.52, CH2Cl2) for 98% ee. IR (Neat)
: 2910, 1720, 1650 cm-1; MS (m/z): 252 (M+); 1H
NMR (CDCl3): δ 2.02 (s, 3 H, OAc), 2.49-2.69
(m, 2 H,CH2), 3.28 (s, 3 H, CH3), 3.35 (s,
3 H, CH3), 4.98-5.06 (m, 2 H,CH2),
5.55-5.73 (m, 2 H, 2 × CH)), 7.12 (m,
1 H, C6H); 13C NMR (CDCl3): δ 21.00
(CH3), 27.75 (CH3), 37.07 (N-CH3),
37.51 (CH2), 69.37 (CH), 111.40 (C-5), 118.33 (CH2), 132.78
(CH), 140.82 (C-6), 151.30 (C=O), 161.71(C=O), 169.83
(C=O). (R)-3b:
Yellow liquid; [α]D
27: +49.42
(c 1.05, CH2Cl2) for 95% ee; IR (Neat):
2920, 1730 and 1590 cm-1; MS (m/z): 252 (M+); 1H
NMR (CDCl3): δ 2.08 (s, 3 H, OAc), 2.57-2.62
(m, 2 H, CH2), 3.99 (s, 3 H, OCH3), 4.01 (s,
3 H, OCH3), 5.03-5.09 (m, 2 H,CH2),
5.64-5.78 (m, 1 H, CH), 5.97 (t, 1 H, J = 4.33
Hz, CH), 8.19 (s, 1 H, Pym-6H); 13C NMR
(CDCl3): δ 20.97 (CH3), 38.58 (CH2),
54.04 (OCH3), 5.76 (OCH3), 68.16 (CH), 113.78
(Pym-C5), 118.36 (CH2), 132.70 (CH), 156.19 (Pym-C6),
164.79 (Pym-C), 168.10 (Pym-C), 169.92 (C=O).
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The acetates of (S)-
alcohols and racemic alcohols were prepared by stirring with excess
(5 equiv) of acetyl chloride and finally washing with 20% Na2CO3 solution.
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