Rhodium(III)-Catalyzed Three-Component Diamination of Bicyclo[1.1.0]butanes via Nitrene Transfer

Rhodium-catalyzed three-component diamination of bicyclo[1.1.0]butanes (BCBs) has been realized for the synthesis of 1,1,3,3-tetrasubstituted cyclobutanes. This ring-opening reaction of BCBs is strain-release-driven, and the trivalent rhodium catalyst facilitates the 1,3-diamination reaction through accommodation of both nucleophilic (aniline) and electrophilic (dioxazolone) nitrogen sources. The reaction exhibits high regio- and diastereoselectivity. The flexibility of this synthetic approach is demonstrated in various downstream transformations.