An alternative mechanism for the cobalt-catalyzed isomerization of terminal alkenes to (Z)-2-alkenes

Angew Chem Int Ed Engl. 2015 Jan 12;54(3):801-4. doi: 10.1002/anie.201409902. Epub 2014 Nov 27.

Abstract

The cobalt-catalyzed selective isomerization of terminal alkenes to the thermodynamically less-stable (Z)-2-alkenes at ambient temperatures takes place by a new mechanism involving the transfer of a hydrogen atom from a Ph2PH ligand to the starting material and the formation of a phosphenium complex, which recycles the Ph2PH complex through a 1,2-H shift.

Keywords: alkenes; cobalt; double-bond migration; isomerization; stereoselectivity.