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

Xiaoyan Lian; Weihao Chen; Liang Dang; Yuchen Li; Chun-Yu Ho

doi:10.1002/anie.201703706

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

Angew Chem Int Ed Engl. 2017 Jul 24;56(31):9048-9052. doi: 10.1002/anie.201703706. Epub 2017 Jun 16.

Authors

Xiaoyan Lian¹, Weihao Chen¹, Liang Dang¹, Yuchen Li¹, Chun-Yu Ho¹

Affiliation

¹ Department of Chemistry, Shenzhen Key Laboratory of Full Spectral Solar Electricity Generation (FSSEG), South University of Science and Technology of China (SUSTC), No. 1088, Xueyuan Road, Shenzhen, China.

PMID: 28547749
DOI: 10.1002/anie.201703706

Abstract

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^II H(OTf) catalysts and cationic Ni^II 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.

Keywords: N-heterocyclic carbenes; geminal olefins; hydroalkenylation; nickel; skipped 1,4-dienes.

Publication types

Research Support, Non-U.S. Gov't