Regioselective anti-Silyllithiation of Propargylic Alcohols

25 July 2022, Version 4
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Among the known hydrosilylation or carbosilylation conditions of alkynes, anti-addition of the two units across the triple bond is considered rare compared to the syn counterpart. For anti-silylative vicinal difunctionalizations, transition-metal catalysts, such as ruthenium or palladium complexes, are generally required. Accordingly, silyl alkali metals have not been employed for those anti-addition transformations. Here we demonstrate that silyllithiums can add across the triple bond of a series of propargylic alkoxides regioselectively in an anti-fashion. Upon treatment with a variety of electrophiles, the tri-substituted alkenyl lithium intermediates were transformed into highly functionalized β-silyl allylic alcohols with high regio-control, eventually providing tri- or tetrasubstituted alkenylsilanes stereoselectively. A classic trick for anti-addition with propargylic alkoxides has transformed anti-silylative functionalizations into a robust and reliable strategy.

Keywords

Silyllithium
Alkenylsilane
Epoxysilane
Silylmetalation
DFT calculation

Supplementary materials

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Description
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Supporting Information
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Experimental procedures, characterization and spectral data for new compounds
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