Access to Alkylsilanes via Nickel-Catalyzed Reductive Alkylsilylation of Acrylonitrile with Carboxylic Acids and Chlorosilanes

Abstract

Transition-metal catalyzed reductive carbosilylation of alkenes with carbon and silyl electrophiles has gained considerable attention for synthetic chemists recently, because it avoids air- and moisture-sensitive pre-prepared organometallic reagents used. However, current carbon electrophiles are limited to alkyl or aryl bromides. Therefore, developing new synthetic approaches by choosing more easily available carbon electrophiles is still in high demand. Herein, we describe a nickel-catalyzed protocol that enables alkylsilylation of acrylonitrile with chlorosilanes and alkyl carboxylic acids via NHPI esters for the construction of various alkylsilanes, in which abundant and easy-accessible carboxylic acids were employed as the new alkyl electrophile sources, overcoming current limitations. This represents the first example of utilizing carboxylic acid as the alkyl reagent in reductive silylative alkylation of alkenes, thus providing a valuable complement to existing methodologies for the synthesis of a variety of organosilanes with diverse structures. Our approach also showcases broad substrate scope (including primary, secondary and tertiary carboxylic acids), good functional group compatibility (tolerating halides, heterocycles, Boc-protected amine, ester, ketone, terminal and internal alkenes, and terminal alkyne) and offers the capability for post-modification of complex agrochemical and pharmaceuticals. In addition, gram-scale reaction further demonstrates the applicable potential of the developed method. Overall, this protocol not only expands the boundaries of reductive difunctionalization reactions of alkenes but also enriches the synthetic toolbox for alkylsilane compounds preparation.

Keywords

Organosilanes / Reductive alkene difunctionalization / Acrylonitrile / Carboyxlic acids / Chlorosilanes / Nickel catalysis / 3d transition metals / Alkenes / Radicals

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