Recent advances in silanecarboxylic acids as versatile reagents for modern organic synthesis

Abstract

Silanecarboxylic acids have evolved from stable chemical curiosities into versatile and practical reagents, a transformation detailed in this review. Initially valued as bench-stable, crystalline carbon monoxide (CO) surrogates, they have enabled safe and controllable CO release for a wide array of transition-metal-catalysed carbonylation reactions. More recently, their role as readily decarboxylative silyl radical precursors under mild photoredox conditions has been unlocked, sparking a paradigm shift in silyl radical chemistry. This review comprehensively summarizes these dual reactivities, covering their applications not only in carbonylations and decarboxylative hydrosilylation, allylation, and C–H silylation but also in emerging transformations such as halogen-atom transfer (XAT) and deaminative processes. By examining key mechanistic insights and representative synthetic applications, we illustrate how these compounds are expanding the synthetic toolbox and addressing long-standing challenges. Finally, we provide a critical outlook on future opportunities and remaining limitations in this rapidly advancing field.