Catalytic Alkoxysilylation of (Hetero)Aryl Bromides with tert-Butyl Alkoxysilyldiazenes

Le résumé fourni par la source

Aryl(alkoxy)silanes are valuable building blocks in organic synthesis and materials science, yet their preparation often relies on stoichiometric organometallic reagents or transition metal-catalyzed methods. Herein, we report a catalytic and transition metal-free alkoxysilylation of (hetero)aryl bromides using tert -butyl-substituted alkoxysilyldiazenes ( t Bu–N=N–SiMe 2 (OR)) as silylating reagents and t BuONa as catalytic initiator. The reaction proceeds under mild conditions and provides direct access to a broad range of functionalized aryl(alkoxy)silanes. Competition experiments and DFT calculations reveal that increasing the electrophilicity of silicon through alkoxy substitution accelerates the key C(sp 2 )–Si bond-forming step relative to SiMe 3 transfer. This enhanced reactivity significantly broadens the substrate scope, enabling the efficient alkoxysilylation of challenging hindered aryl bromides and those bearing electrophilic functional groups.

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