FeCl2 Catalyzed Three-Component Reactions of Phospholes, Pyrrolidine, and Ketones (Aldehydes): Chemoselective Synthesis of 1-Phosphafulvenes

We have developed an unprecedented approach for the synthesis of transient 1-phosphafulvenes through three component reactions of phospholes. The generation of 1-phosphafulvenes was demonstrated by in situ [6 + 4] cycloaddition with 2H-phospholes and [6 + 6] self-dimerization. The [6 + 4] and [6 + 6] reaction pathway could be modulated by the starting ketones and aldehydes. The construction of 1-phosphafulvenes is illustrated by a proposed mechanism combining nucleophilic addition of phospholide to the iminium or isomerized azomethine ylide and a [1,5]-shift of phosphole.