Dirhodium-catalyzed transformations, not limited to carbene and nitrene transfer reactions, are reviewed, including cycloisomerization, hetero-Diels–Alder (HDA) reactions, ene reactions, arylation, radical oxidation reactions and C–H activation, etc.
The underlying discrimination mechanism and the origins of catalyst-dependent selectivity are disclosed for divergent cycloaddition reactions.
In situ-formed guanidinium creates a hydrogen bonding network that enabled stereo-determinant protonation of an enol/ylide species for the N–H insertion product.
The three-component reaction of the diazo compound, azide and allylboronate for preparation of homoallylic amine derivatives was explored, and Rh2(esp)2 was utilized as the optimal catalyst.
DFT calculations reveal the detailed mechanism and elucidate the roles of Rh and amine catalysis, as well as the origins of regio- and stereoselectivity in alkyne–cyclopropene reassembly.