Medium and Large N -Heterocycle Formation via Allene Hydroamination with a Bimetallic Rh(II) Catalyst.

We report the synthesis of a 2-phosphinoimidazole-derived bimetallic Rh(II) complex that enables intramolecular allene hydroamination to form 7- to 10-member rings in high yield. Monometallic Rh complexes, in contrast, fail to achieve any product formation. We demonstrate a broad substrate scope for formation of various N -heterocycles. Macrocyclizations that form 11- to 15-member N -heterocycles are also demonstrated. Mechanistic studies suggest that the reaction proceeds via reversible allene insertion with a Rh-hydride followed by C-N bond-forming reductive elimination. We hypothesize that the reactivity observed with our catalyst vs monometallic Rh complexes is derived from the bimetallic nature of our complex.