Nickel-Catalyzed Reductive Cross-Coupling of Alkyl Bromides and Chlorosilanes

Abstract

A novel nickel-catalyzed highly selective reductive cross-coupling of alkyl bromides and chlorosilanes to construct the C–Si bond has been developed. Under benign reaction conditions, a series of structurally interesting organosilanes can be accessed without Ni-catalyzed isomerization. The utility of this chemistry is illustrated by further transformations of the product. Moreover, the radical mechanism of the reaction is illustrated by control experiments.

Recent Advances in Transition-Metal-Catalyzed C–H Alkylation with Three-Membered Rings

“…In earlier years, the traditional Friedel–Crafts reaction or radical alkylation was developed and is still widely used in modern academic and industrial production . In the 1980s, cross-coupling reactions of organometallic substrates with alkyl electrophiles have emerged as an especially robust alternative for the construction of oxygen- or nitrogen-containing heterocycles . Even today, the site-selective alkylation of (hetero)­arenes still largely employs these methods.…”

Theoretical Study on Si−Cl Bond Activation in Pd‐Catalyzed Cross‐Coupling of Chlorosilanes with Organoaluminum

“…[3] Recent development in this field has enabled access to a variety of organosilicon compounds from chlorosilanes in a low number of steps, which are not readily obtainable from the conventional hydrosilylation and ionic coupling of highly nucleophilic organometallic reagents. [2,[4][5][6][7][8][9][10][11] However, few theoretical studies have focused on the mechanisms of these cross-coupling reactions. [12] In 1988, Tanaka reported the reaction of Pt(0) complexes with trimethylbromosilane and trimethyliodosilane as the first examples of the oxidative addition reactions of halosilanes.…”

Nickel-Catalyzed Reductive Csp3–Ge Coupling of Alkyl Bromides with Chlorogermanes

“…Our group has an ongoing interest in the development of unconventional coupling partners for cross-electrophile coupling . Very recently, we and others have extended this chemistry to reductive C–Si couplings . In 2021, we reported the first reductive Csp 2 –Ge coupling reaction and demonstrated the power of cross-electrophile coupling in the preparation of aryl and vinylgermanes (Scheme b) .…”