Origins of ligand-controlled diastereoselectivity in dirhodium-catalysed direct amination of aliphatic C(sp(3))-H bonds

摘要

The mechanism and origins of ligand-controlled stereoselectivity of dirhodium (Rh2L4, L = OAc, S-tertPTTL)-catalysed intramolecular aliphatic C(sp(3))-H aminations have been explored using DFT calculations. Both catalytic cycles occur via the formation of Rh-2 = nitrene radical species, intramolecular H-abstraction and radical rebound. The origins of diastereoselectivity are revealed via distortion/interaction and noncovalent interaction analysis.