Designing Cross‐Coupling Reactions using Aryl(trialkyl)silanes

Organo(trialkyl)silanes have several advantages, including high stability, low toxicity, good solubility, easy handling, and ready availability compared with heteroatom‐substituted silanes. However, methods for the cross‐coupling of organo(trialkyl)silanes are limited, most probably because of their exceeding robustness. Thus, a practical method for the cross‐coupling of organo(trialkyl)silanes has been a long‐standing challenging research target. This article discusses how aryl(trialkyl)silanes can be used in cross‐coupling reactions. A pioneering example is CuII catalytic conditions with the use of electron‐accepting aryl‐ or heteroaryl(triethyl)silanes and aryl iodides. The reaction forms biaryls or teraryls. This design concept can be extended to Pd/CuII‐catalyzed cross‐coupling polymerization reactions between such silanes and aryl bromides or chlorides and to CuI‐catalyzed alkylation using alkyl halides. In plain Si‐ght! This concept article focuses on transition‐metal‐catalyzed cross‐coupling reactions using organo(trialkyl)silanes. Mainly, we discuss methods for the practical activation of robust carbon–trialkylsilyl bonds and our recent developments in aryl–aryl and aryl–alkyl bond‐forming cross‐coupling reactions of aryl(trialkyl)silanes with aryl or alkyl halides. n‐Hex=n‐hexyl, Ts=tosyl.