Switch to Allylic Selectivity in Cobalt-Catalyzed Dehydrogenative Heck Reactions with Unbiased Aliphatic Olefins

A unique C–H allylation has been discovered with unbiased aliphatic olefins. An intimate M–L affiliation between a high-valent cobalt catalyst and amino-quinoline derived benzamides has been found to be crucial for this unprecedented selectivity. An exemplary set of aliphatic olefins, high yields coupled with excellent regio- and stereoselectivity, and wide functional group tolerances are noteworthy. In addition, a catalytically competent organometallic Co­(III) species has been identified through X-ray crystallography. This study is expected to facilitate new synthetic designs toward unconventional allylic selectivity with aliphatic olefins.