Ligand-Controlled Cobalt-Catalyzed Regiodivergent and Stereoselective Ring-Opening Isomerization of Vinyl Cyclopropanes.

A ligand-controlled regiodivergent and stereoselective ring-opening isomerization of vinylcyclopropane was developed with cobalt catalysis. Employing the commercially available Xantphos ligand, the reactions afforded exclusively linear-type 1,3-dienes as the products. Interestingly, when switching the ligand to an amido-diphosphine ligand (PNP), branched-type 1,3-dienes were obtained with high regioselectivity and stereoselectivity. Preliminary mechanistic investigations suggested that a π-allyl metal and a metal-hydride species are involved as key intermediates in the two transformations, respectively.