title: Catalytic Asymmetric Arylation of α-Aryl-α-diazoacetates with Aniline Derivatives.
abstract: The asymmetric arylation of diazo compounds with aniline derivatives cooperatively catalyzed by an achiral dirhodium complex and a chiral spiro phosphoric acid is reported. The reaction provides a new method for the facile synthesis of α-diarylacetates, versatile building blocks with a diaryl tertiary chiral center, in good yields (up to 95%) with high enantioselectivities (up to 97% ee). Preliminary mechanistic studies suggest that the arylation reaction proceeds via a stepwise process, in which the enantioselectivity is controlled by a chiral spiro phosphoric acid-promoted proton shift in a zwitterionic intermediate. This work represents the first asymmetric intermolecular C(sp(2))-H bond insertion reaction with arenes.
authors.affiliation: †State Key Laboratory and Institute of Elemento-Organic Chemistry, ‡Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China.
authors.forename: Bin
authors.initials: B
authors.lastname: Xu
authors.affiliation: †State Key Laboratory and Institute of Elemento-Organic Chemistry, ‡Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China.
authors.forename: Mao-Lin
authors.initials: ML
authors.lastname: Li
authors.affiliation: †State Key Laboratory and Institute of Elemento-Organic Chemistry, ‡Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China.
authors.forename: Xiao-Dong
authors.initials: XD
authors.lastname: Zuo
authors.affiliation: †State Key Laboratory and Institute of Elemento-Organic Chemistry, ‡Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China.
authors.forename: Shou-Fei
authors.initials: SF
authors.lastname: Zhu
authors.affiliation: †State Key Laboratory and Institute of Elemento-Organic Chemistry, ‡Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China.
authors.forename: Qi-Lin
authors.initials: QL
authors.lastname: Zhou
mesh_terms: D000085:Acetates / Q000737:chemistry*; D000814:Aniline Compounds / Q000737:chemistry*; D001391:Azo Compounds / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D006841:Hydrocarbons, Aromatic / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D010756:Phosphoric Acids / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000085:Acetates; D000814:Aniline Compounds; D001391:Azo Compounds; D006841:Hydrocarbons, Aromatic; D010756:Phosphoric Acids; D012238:Rhodium; C030242:phosphoric acid; C023650:aniline