title: Catalytic asymmetric functionalization of aromatic C-H bonds by electrophilic trapping of metal-carbene-induced zwitterionic intermediates.
abstract: Asymmetric functionalization of aromatic C-H bonds of N,N-disubstituted anilines with diazo compounds and imines is reported for the efficient construction of α,α-diaryl benzylic quaternary stereocenters in good yields with high diastereoselectivities and excellent enantioselectivities. This Rh(II)/chiral phosphoric acid cocatalyzed transformation is proposed to proceed through a metal-carbene-induced zwitterionic intermediate which undergoes electrophilic trapping. To the best of our knowledge, this is the first asymmetric example of metal carbene-induced intermolecular functionalization of aryl C-H bonds.
authors.affiliation: Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development; Department of Chemistry, East China Normal University, 3663, North Zhongshan Road, Shanghai, 200062 (China).
authors.forename: Shikun
authors.initials: S
authors.lastname: Jia
authors.forename: Dong
authors.initials: D
authors.lastname: Xing
authors.forename: Dan
authors.initials: D
authors.lastname: Zhang
authors.forename: Wenhao
authors.initials: W
authors.lastname: Hu
mesh_terms: D002384:Catalysis; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: C030011:carbene; D012238:Rhodium; D008697:Methane
keywords: CH activation; asymmetric catalysis; carbenes; rhodium; zwitterions