Catalytic Oxidative Ligand Transfer of Rh-Carbynoids and Alkyl Iodides

Herein, we disclose the first catalytic generation of alkyl–I(III) Rh(II)-carbynoids via oxidative ligand transfer between alkyl iodides and aryl–I(III) Rh(II)-carbynoids. When homoallylic iodides were used, alkyl–I(III) Rh(II)-carbynoids evolved through a diastereoselective cyclopropanation that led to highly electrophilic bicyclic alkyl–I(III) species. We observed that the latter species reacted with a plethora of nucleophiles, enabling access to a valuable class of cyclopropanes that were converted to housanes.