Nickel‐Catalyzed Stereo‐ and Enantioselective Cross‐Coupling of gem‐Difluoroalkenes with Carbon Electrophiles by C−F Bond Activation. (23rd December 2021)

• Record Type: Journal Article
• Authors: Zhu, Ziqi; Lin, Lin; Xiao, Jieshuai; Shi, Zhuangzhi
• Is Part Of: Angewandte Chemie. Volume 134:Number 6(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-12-23
• Subjects: Cross-coupling -- Enantioselectivity -- gem-Difluoroalkenes -- Nickel -- Stereoselectivity; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202113209
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Stereo‐ and enantioselective cross‐electrophile coupling involving C−F bond activation is reported. Treatment of gem‐difluoroalkenes with racemic benzyl electrophiles in the presence of a chiral nickel complex using B2 pin2 as a stoichiometric reductant allows the construction of a C(sp 2 )−C(sp 3 ) bond under mild conditions, affording a broad range of monofluoroalkenes bearing stereogenic allylic centers. Initial mechanistic studies indicate that a radical chain pathway may be operating, wherein the ester group in the gem‐difluoroalkene promotes C−F bond activation through oxidative addition to a Ni species . Abstract : A cross‐electrophile coupling between gem ‐difluoroalkenes and benzyl electrophiles proceeds through nickel‐catalyzed chelation‐assisted C−F bond activation and shows excellent stereoselectivity and enantioselectivity.