(NHC)NiH-Catalyzed Intermolecular Regio- and Diastereoselective Cross-Hydroalkenylation of Endocyclic Dienes with α-Olefins.

Highly selective cross-hydroalkenylations of endocyclic 1,3-dienes at the least substituted site with α-olefins were achieved with a set of neutral (NHC)Ni H(OTf) catalysts and cationic Ni catalysts with a novel NHC ligand. Under heteroatom assistance, skipped dienes were obtained in good yields, often from equal amounts of the two substrates and at a catalyst loading of 2-5 mol %. Rare 4,3-product selectivity (i.e., with the H atom at C4 and the alkenyl group at C3 of the diene) was observed, which is different from the selectivity of known dimerizations of α-olefins with both acyclic Co and Fe systems. The influence of the various substituents on the NHC, 1,3-diene, and α-olefin on the chemo-, regio-, and diastereoselectivity was studied. High levels of chirality transfer were observed with chiral cyclohexadiene derivatives.