Baylis-Hillman Acetates in Synthesis: Copper(I)/tert-Butyl Hydroperoxide Promoted One-Pot Oxidative Intramolecular Cyclization Protocol for the Preparation of Pyrrole-Fused Compounds and the Formal Synthesis of (±)-Crispine A

A convenient one‐pot protocol for the synthesis of benzo‐fused and indole‐fused indolizines from Baylis–Hillman acetates was developed. This strategy involves CuBr/tert‐butyl hydroperoxide promoted oxidation, intramolecular cyclization, and aromatization as key steps. The efficacy of this methodology was demonstrated by the formal synthesis of (±)‐crispine A, a biologically active molecule. A one‐pot, four‐step strategy involving alkylation, oxidation, intramolecular cyclization, and aromatization is developed for the synthesis of pyrrole‐fused tri‐ and tetracyclic compounds by using Baylis–Hillman acetates as the starting materials. A formal synthesis of biologically active (±)‐crispine A is also achieved. EWG = electron‐withdrawing group.