In 2012, we described a palladium-catalyzed synthesis of allyl silanes via the direct silylation of terminal olefins bearing allylic hydrogen. While this silyl�Heck reaction provided rapid entry into an important class of nucleophilic silanes, the yields in the transformation were only modest (ca. 60-70%) due to competitive isomerization of the alkene starting material. Herein, we present a second-generation catalyst that largely overcomes these side-reactions and allow allyl silanes to be prepared good to excellent yields. We will discuss the development of the second-generation catalyst, the steric and electronic properties of the effective ligands, and scope of the improved process for allyl silane synthesis.

High yielding allylic-silylation reactions using a second-generation silyl-Heck catalyst

247th National Meeting (2014)

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