Nickel-catalyzed regio- and diastereoselective hydroarylative and hydroalkenylative cyclization of 1,6-dienes

Abstract

By using methanol as the hydrogen source and commercially available nickel complex as the catalyst, the hydroarylative and hydroalkenylative cyclization of unsymmetrically substituted 1,6-dienes with organoboronic acid was developed to afford products with high regio- and diastereoselectivities.

Understanding the mechanism and origins of stereoconvergence in nickel-catalyzed hydroarylation of 1,3-dienes with aryl boronates

“…9 Subsequently, a range of Ni-catalysed redox-neutral hydroarylations of alkenes/1,3-dienes and arylboronic acids using diverse alcohols as the hydrogen source have been established by numerous research groups. [10][11][12][13][14][15][16][17][18][19][20] Among these noteworthy developments, the Mei group and Zhou group independently developed the Ni-catalysed enantioselective hydroarylation of olefins by employing chiral N,N and P,N bidentate ligands. 11,13 However, the highly enantioselective hydroarylation of 1,3-dienes still remains a key challenge in this field.…”

Enantioselective Hydroesterificative Cyclization of 1,6-Enynes to Chiral γ-Lactams Bearing a Quaternary Carbon Stereocenter

“…Compared with the well-established industrial application of nonasymmetric alkoxycarbonylation, the development of corresponding asymmetric variant is rather sluggish, probably due to the difficulty of simultaneously controlling the chemo-, regio-, and enantioselectivities under a nonbeneficial reaction temperature and high CO pressure . Following our interest in catalytic asymmetric carbonylation and cyclization reactions, we envisioned integrating the challenging but rewarding alkoxycarbonylation with enyne cyclization reaction would offer a novel entry to chiral heterocyclic compounds containing both a carboxylic ester group and a quaternary carbon center with high efficiency of carbon–carbon/heteroatom bond formation.…”