title: Remarkable enhancement of enantioselectivity in the asymmetric conjugate addition of dimethylzinc to (Z)-nitroalkenes with a catalytic [(MeCN)₄Cu]PF₆-Hoveyda ligand complex.
abstract: An enantioselective copper-catalyzed asymmetric conjugate addition of Me2Zn to (Z)-nitroalkenes led to the formation of all-carbon quaternary stereogenic centers with high stereoselectivity. The key features of the new method are the unprecedented use of [(MeCN)4Cu]PF6 in conjunction with the Hoveyda ligand L1 and the use of (Z)-nitroalkene substrates so that undesired nitroalkene isomerization is minimized and enantioselectivity is enhanced dramatically. We also describe a novel, practical, and highly (Z)-selective nitroalkene synthesis.
authors.affiliation: Chemical Development, Boehringer Ingelheim Pharmaceuticals, Inc. 900 Ridgebury Road, Ridgefield, CT 06877 (USA). xingzhong.zeng@boehringer-ingelheim.com.
authors.forename: Xingzhong
authors.initials: X
authors.lastname: Zeng
authors.forename: Joe J
authors.initials: JJ
authors.lastname: Gao
authors.forename: Jinhua J
authors.initials: JJ
authors.lastname: Song
authors.forename: Shengli
authors.initials: S
authors.lastname: Ma
authors.forename: Jean-Nicolas
authors.initials: JN
authors.lastname: Desrosiers
authors.forename: Jason A
authors.initials: JA
authors.lastname: Mulder
authors.forename: Sonia
authors.initials: S
authors.lastname: Rodriguez
authors.forename: Melissa A
authors.initials: MA
authors.lastname: Herbage
authors.forename: Nizar
authors.initials: N
authors.lastname: Haddad
authors.forename: Bo
authors.initials: B
authors.lastname: Qu
authors.forename: Keith R
authors.initials: KR
authors.lastname: Fandrick
authors.forename: Nelu
authors.initials: N
authors.lastname: Grinberg
authors.forename: Heewon
authors.initials: H
authors.lastname: Lee
authors.forename: Xudong
authors.initials: X
authors.lastname: Wei
authors.forename: Nathan K
authors.initials: NK
authors.lastname: Yee
authors.forename: Chris H
authors.initials: CH
authors.lastname: Senanayake
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D002851:Chromatography, High Pressure Liquid; D003300:Copper / Q000737:chemistry*; D007536:Isomerism; D008024:Ligands; D009584:Nitrogen / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D008024:Ligands; D009942:Organometallic Compounds; D003300:Copper; C511262:dimethylzinc; D009584:Nitrogen
keywords: asymmetric conjugate addition; copper; nitroalkenes; quaternary stereocenters; zinc