Synthesis of Nonracemic 2-Vinyl-monoprotected 1,3-Diols from the Reactions of Chiral Allylstannanes with Aldehydes

References

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• 1991 . These were results presented at the 201st American Chemical Society National Meeting . April 14–19 1991 , Atlanta, GA. A typical reaction procedure follows. 1-(p-nitrophenyl)-2-vinyl-3-benzyloxybutan-1-ol, 1C: To a solution of (0.16 g, 0.34 mmol) allylstannane III and (0.12 g, 0.81 mmol) p-nitrobenzaldehyde in 3 ml CH2Cl2 at − 78 °C was added (0.10 ml, 0.81 mmol) BF3·Et2O. The solution was allowed to stir for 1.5 hr at − 78 °C, then ether was added, and the reaction was quenched with sat. NaHCO3 solution. The organic layer was washed with sat. NaCl solution and dried over MgSO4. The crude product was purified by column chromatography (10% EtOAc/Hex) to give (0.068 g, 0.21 mmol) the title compound as a colorless oil (61% yield). [α]D20 = +4.2° (EtOH, c=0.1). IR (neat): 3400, 3080, 2956, 2854, 1457, 1344, 699 cm−1. 1 H NMR (CDCl3): δ 8.11 (d, J = 8.7 Hz, 2H), 7.36 (s, 5 Hz), 7.36 (m, 2H), 5.23–4.80 (m, 2H), 5.23 (ddd, J = 9.1, 9.5, 17.1 Hz, 1H), 4.76 (d, J = 11.3 Hz, 1H), 4.68 (d, J = 5.3 Hz, 1H), 4.49 (d, J = 11.3 Hz, 1H), 3.76 (dq, J = 6.1, 9.1 Hz, 1H), 2.49 (ddd, J = 9.1, 9.1, 9.1 Hz, 1H), 1.26 (d, J = 6.1 Hz, 3H)
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• Ja,b ≈ Jb,c ≈ Jb,d ≈ 9.1 Hz
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• The anti-anti stereochemistry of the products is not to be confused with the syn (erythro)-selective process of the reactions between allylstannanes and aldehydes in the presence of Lewis acid. In fact, both anti-anti and anti-syn isomers are from syn-selective process, which is in accord with literature precedents.1,2
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