Visible-Light-Induced Acylsilylation of Nitrosoarenes for Synthesis of <i>N</i> -Arylhydroxamic Acid Silicon Esters

A visible-light-induced acylsilylation of nitrosoarenes with acylsilanes has been developed under transition-metal-free conditions. This reaction proceeds via a photoinduced [1,2]-Brook rearrangement of acylsilanes to generate nucleophilic siloxycarbenes, which add to the electrophilic nitrogen atom of nitrosoarenes, affording a range of <i>N</i>-arylhydroxamic acid silicon esters. Control experiments support a singlet carbene pathway. This method is operationally simple, proceeds under mild conditions, and exhibits a broad substrate scope, offering an atom-economical and practical approach to an important class of hydroxamic acid derivatives.