Stereoselective intramoleculer allylsilane additions to chiral aldehydes

Reetz, M. T.; Jung, A.; Bolm, C.

doi:10.1016/S0040-4020(01)86643-6

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Stereoselective intramoleculer allylsilane additions to chiral aldehydes

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Reetz, M. T., Jung, A., & Bolm, C. (1988). Stereoselective intramoleculer allylsilane additions to chiral aldehydes. Tetrahedron, 44(13), 3889-3898. doi:10.1016/S0040-4020(01)86643-6.

Cite as: https://hdl.handle.net/21.11116/0000-000E-7CF3-5

Abstract

The sense of 1,3-asymmetric induction in the TiCl₄ mediated allylailane addition of O-(allyl)silyl protected aldehydes 14 is opposite (>62;90% syn selectivity) to that of the previously reported reaction of the 0-benzyl protected analogs 7 with allyltrimethylsilane (90% anti selectivity). Crossover experiments show that strict intramolecularity pertains, suggesting an intramolecular allylsilane addition as depicted in 15. Surprisingly, the switch from TiCl₄ to SnCl₄ results in the reversal of diastereofacial selectivity and in an intermolecular allyl transfer mechanism. α-Chiral β-silyloxy aldehydes of the type 35 are not very well suited for stereoselective allylations.