81372-28-3Relevant academic research and scientific papers
Biphilic organophosphorus catalysis: Regioselective reductive transposition of allylic bromides via PIII/PV redox cycling
Reichl, Kyle D.,Dunn, Nicole L.,Fastuca, Nicholas J.,Radosevich, Alexander T.
supporting information, p. 5292 - 5295 (2015/05/13)
We report that a regioselective reductive transposition of primary allylic bromides is catalyzed by a biphilic organophosphorus (phosphetane) catalyst. Spectroscopic evidence supports the formation of a pentacoordinate (σ5-P) hydridophosphorane as a key reactive intermediate. Kinetics experiments and computational modeling are consistent with a unimolecular decomposition of the σ5-P hydridophosphorane via a concerted cyclic transition structure that delivers the observed allylic transposition and completes a novel PIII/PV redox catalytic cycle. These results broaden the growing repertoire of reactions catalyzed within the PIII/PV redox couple and suggest additional opportunities for organophosphorus catalysis in a biphilic mode.
