NHC-Ni catalyzed enantioselective synthesis of 1,4-dienes by cross-hydroalkenylation of cyclic 1,3-dienes and heterosubstituted terminal olefins

Yang Chen; Liang Dang; Chun-Yu Ho

doi:10.1038/s41467-020-16139-2

NHC-Ni catalyzed enantioselective synthesis of 1,4-dienes by cross-hydroalkenylation of cyclic 1,3-dienes and heterosubstituted terminal olefins

Nat Commun. 2020 May 8;11(1):2269. doi: 10.1038/s41467-020-16139-2.

Authors

Yang Chen¹, Liang Dang², Chun-Yu Ho³

Affiliations

¹ Shenzhen Grubbs Institute, Guangdong Provincial Key Laboratory of Catalysis, Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, 518055, China.
² Shenzhen Grubbs Institute, Guangdong Provincial Key Laboratory of Catalysis, Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, 518055, China. dangl3@sustech.edu.cn.
³ Shenzhen Grubbs Institute, Guangdong Provincial Key Laboratory of Catalysis, Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, 518055, China. jasonhcy@sustech.edu.cn.

Abstract

Enantioenriched 1,4-dienes are versatile building blocks in asymmetric synthesis, therefore their efficient synthesis directly from chemical feedstock is highly sought after. Here, we show an enantioselective cross-hydroalkenylation of cyclic 1,3-diene and hetero-substituted terminal olefin by using a chiral [NHC-Ni(allyl)]BAr^F catalyst. Using a structurally flexible chiral C₂ NHC-Ni design is key to access a broad scope of chiral 1,4-diene 3 or 3' with high enantioselectivity. This study also offers insights on how to regulate chiral C₂ NHC-Ni(II) 1,3-allylic shift on cyclic diene 1 and to build sterically more hindered endocyclic chiral allylic structures on demand.

Publication types

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