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
Abstract
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 C 2 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 C 2 NHC-Ni(II) 1,3-allylic shift on cyclic diene 1 and to build sterically more hindered endocyclic chiral allylic structures on demand.
Topics & Concepts
Enantioselective synthesisDieneAllylic rearrangementSteric effectsOlefin fiberCatalysisChemistryCombinatorial chemistryStereochemistryOrganic chemistryNatural rubberN-Heterocyclic Carbenes in Organic and Inorganic ChemistryAsymmetric Hydrogenation and CatalysisSynthetic Organic Chemistry Methods