Single-electron N-heterocyclic carbene (NHC) catalysis has gained attention recently for the synthesis of CÀC bonds. Guided by density functional theory and mechanistic analyses, we report the light-driven synthesis of aliphatic and aamino ketones using single-electron NHC operators. Computational and experimental results reveal that the reactivity of the key radical intermediate is substrate-dependent and can be modulated through steric and electronic parameters of the NHC. Catalyst potential is harnessed in the visible-light driven generation of an acyl azolium radical species that undergoes selective coupling with various radical partners to afford diverse ketone products. This methodology is showcased in the direct late-stage functionalization of amino acids and pharmaceutical compounds, highlighting the utility of single-electron NHC operators.

A novel strategy for the stereospecific Pd-catalyzed acylative cross-coupling of enantiomerically enriched alkylboron compounds has been developed. The protocol features an extremely high level of enantiospecificity to allow facile access to synthetically challenging and valuable chiral ketones and carboxylic acid derivatives. The use of a sterically encumbered and electronrich phosphine ligand proved to be crucial for the success of the reaction. Furthermore, on the basis of experimental and computational studies, a unique mechanism for the transmetalation, assisted by the noncovalent interactions of the C(sp 3 )-based organoboron reagent, has been identified.

A site-selective annulation reaction between cyclic α-chloro eneformamides and cyclic anhydrides which provides direct and modular access to pharmaceutically pertinent izidinones and isoquinolones, is presented.