Rapid Methylation of Aryl Bromides Using Air‐Stable DABCO‐Bis(Trimethylaluminum) via Nickel Metallaphotoredox Catalysis
Abstract
Abstract We report a metallaphotocatalytic strategy for the selective methylation of (hetero)aryl bromides via nickel‐catalyzed cross‐coupling with bis(trimethylaluminum)‐1,4‐diazabicyclo[2.2.2]octane (DABAl‐Me₃), as a commercially available, air‐stable, and non‐pyrophoric aluminum‐based reagent. The method enables a fast, robust, and scalable methylation protocol that broadly accommodates various functional groups while preventing protodehalogenation. Mechanistic studies confirm the unprecedented generation of methyl radicals from an organo‐aluminum precursor under photoredox conditions, bypassing the limitations of conventional two‐electron pathways. This work expands the toolbox of practical radical precursors and provides a streamlined approach for selective C(sp 2 )─CH 3 bond formation.
Article Details
Authors (9)
Jonas Djossou
Flow Chemistry Group, van ’t Hoff Institute for Molecular Sciences (HIMS) University of Amsterdam Amsterdam 1098 XH The Netherlands
Andrea Aloia
Flow Chemistry Group, van ’t Hoff Institute for Molecular Sciences (HIMS) University of Amsterdam Amsterdam 1098 XH The Netherlands
Luca Capaldo
Demi D. Snabilié
Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands
Morgan Regnier
Flow Chemistry Group, van ’t Hoff Institute for Molecular Sciences (HIMS) University of Amsterdam Amsterdam 1098 XH The Netherlands
Jasper H.A. Schuurmans
Flow Chemistry Group, Van’t Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, Amsterdam 1098 XH, The Netherlands
Antonio Monopoli
Chemistry Department University of Bari Aldo Moro Via Orabona 4 Bari 70125 Italy
Bas de Bruin
Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands
Timothy Noël
Flow Chemistry Group, Van’t Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, Amsterdam 1098 XH, The Netherlands