Expanding the Ligand Framework Diversity of Carbodicarbenes and Direct Detection of Boron Activation in the Methylation of Amines with CO₂

Abstract

Abstract A simple and convergent synthetic strategy used to increase the diversity of the carbodicarbene ligand framework through incorporation of unsymmetrical pendant groups is reported. Structural analysis and spectroscopic studies of ligands and their Rh complexes are reported. Reactivity studies reveal carbodicarbenes as competent organocatalysts for amine methylation using CO 2 as a synthon. A unique BH‐activated boron–carbodicarbene complex was isolated as a reaction intermediate, providing mechanistic insight into the CO 2 functionalization process.