Formal Lossen Rearrangement/Alkenylation or Annulation Cascade of Heterole Carboxamides with Alkynes Catalyzed by CpRhIII Complexes with Pendant Amides

It has been established that a cyclopentadienyl (Cp) Rh^III complex with two aryl groups and a pendant amide moiety catalyzes the formal Lossen rearrangement/alkenylation cascade of N-pivaloyl heterole carboxamides with internal alkynes, leading to alkenylheteroles. Interestingly, the use of sterically demanding internal alkynes afforded not the alkenylation but the 3+2] annulation products (5,5]-fused heteroles). In these reactions, the pendant amide moiety of the CpRh^III complex may accelerate the formal Lossen rearrangement. The use of five-membered heteroles may deter reductive elimination to form strained 5,5]-fused heteroles; instead, protonation proceeds to give the alkenylation products. Bulky alkyne substituents accelerate the reductive elimination to allow the formation of the 5,5]-fused heteroles.