Frontispiece: Formal Lossen Rearrangement/[3+2] Annulation Cascade Catalyzed by a Modified Cyclopentadienyl RhIII Complex

Abstract

A cyclopentadienyl RhIII complex with two phenyl groups and a pendant amide moiety catalyzes the formal Lossen rearrangement/[3+2] annulation cascade of N-pivaloyl-benzamides and acrylamides with alkynes leading to substituted indoles and pyrroles. Mechanistic studies reveal that this cascade reaction proceeds via C−H bond cleavage, alkyne insertion, and formal Lossen rearrangement. The use of CpARhIII in place of commercially available Cp*RhIII can alter the reaction pathway. See more in the Communication on page 5723 ff.