Site- and Regioselective Monoalkenylation of Pyrroles with Alkynes via Cp*CoIII Catalysis.

A site-, regio-, syn-, and monoselective alkenylation of dimethylcarbamoyl-protected pyrroles proceeded using a catalytic amount of [Cp*Co(CH3CN)3](SbF6)2 and KOAc. A variety of internal alkynes with several functional groups and a terminal alkyne afforded hydropyrrolation products in a selective manner in good to excellent yield. The site-selectivity (C2/C5 selectivity) observed for C3-substituted pyrroles is noteworthy because Cp*RhIII-catalyzed conditions afforded only a moderate yield and low selectivity. The conditions described here provide general and straightforward access to unsymmetrically mono- and disubstituted pyrrole derivatives.