title: Rh(II)-catalyzed reaction of alpha-diazocarbonyl compounds bearing beta-trichloroacetylamino substituent: C-H insertion versus 1,2-H shift.
abstract: The Rh(II)-carbene reaction is dramatically affected by the neighboring substituents. If the neighboring substituent is an OH group, a1,2-H shift is the exclusive pathway. If it is an OAc group, a 1,2-acetoxy migration is observed. If it is p-toluenesulfonyl group, 1,3 and 1,5-C-H insertion are the major pathways, and the 1,2-H shift is completely suppressed. If the adjacent substituent is a trichloroacetyl amino group, 1,5-C-H insertion competes with the 1,2-hydride shift, and no 1,3-C-H insertion can be observed. Both electronic and steric factors are responsible for the switching of the Rh(II)-carbene reaction pathway. The highly stereoselective 1,5-C-H insertions in Rh(II)-catalyzed reaction of alpha-diazocarbonyl compounds, bearing beta-trichloroacetylamino substituent, can be utilized as a novel way to synthesize five-membered cyclic beta-amino acid derivatives.
authors.affiliation: Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, P.R. China.
authors.forename: Zhenhua
authors.initials: Z
authors.lastname: Zhang
authors.forename: Weifeng
authors.initials: W
authors.lastname: Shi
authors.forename: Jian
authors.initials: J
authors.lastname: Zhang
authors.forename: Bo
authors.initials: B
authors.lastname: Zhang
authors.forename: Bingge
authors.initials: B
authors.lastname: Liu
authors.forename: Yiyang
authors.initials: Y
authors.lastname: Liu
authors.forename: Bo
authors.initials: B
authors.lastname: Fan
authors.forename: Fengping
authors.initials: F
authors.lastname: Xiao
authors.forename: Feng
authors.initials: F
authors.lastname: Xu
authors.forename: Jianbo
authors.initials: J
authors.lastname: Wang
mesh_terms: D000596:Amino Acids / Q000737:chemistry; D001391:Azo Compounds / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008968:Molecular Conformation; D012238:Rhodium / Q000737:chemistry*
chemical_list: D000596:Amino Acids; D001391:Azo Compounds; C030011:carbene; D012238:Rhodium; D008697:Methane