Thermocatalytic Dehydrogenation‐Enabled Arene‐Alkane Couplings†

Comprehensive Summary The direct use of non‐prefunctionalized arene and alkane as the starting materials to construct C aryl −C alkyl bond is an unfulfilled target and approaches to this challenge rarely surface in methodology studies. Current methods for thermocatalytic arene‐alkane couplings (AAC) occur with specific substrates and/or inconvenient reagents. Herein, we report a one‐pot relay bicatalysis system for AAC involving (pincer)Ir‐catalyzed alkane transfer dehydrogenation and Fe(OTf) 3 ‐catalyzed olefin hydroarylation. This system exhibits broad scope and is particularly effective for alkylation of arenes with arylalkanes to form 1,1‐diarylalkanes with high chemo‐ and regioselectivity, making it potentially useful for late‐stage alkylation of complex molecules. Experimental mechanistic data provide a view into the factors controlling the regioselectivity. Finally, the strategy of dehydrogenation‐enabled arene‐alkane couplings has been successfully extended to a tandem catalysis by using a heterogeneous olefin hydroarylation catalyst.