Deaminative C( <i>sp</i> ³ )─C( <i>sp</i> ³ ) Cross-Coupling of Benzylamines with Alcohols and Carboxylic Acids via Radical Sorting

High Resolution Image Download MS PowerPoint Slide Benzylamines represent a promising yet underexplored class of building blocks in C(sp 3 )─C(sp 3 ) bond formation. The scarcity of deaminative coupling methods of benzylamines with other ubiquitous native functionalities, such as alcohols and carboxylic acids, has constrained their synthetic utility. Herein, we report two metallaphotoredox C(sp 3 )─C(sp 3 ) cross-coupling reactions that merge structurally diverse benzylamines with carboxylic acids and 3° alcohols. In both transformations, the key bond-forming step proceeds via a Fe-porphyrin-catalyzed S H 2 radical sorting pathway. Both reactions exhibit broad substrate scope, with their synthetic utility further highlighted in the synthesis of complex, biologically active compounds, semisaturated aromatic scaffolds, and enantiopure pyrrolidine derivatives.