title: Stereoselective 1,3-insertions of rhodium(II) azavinyl carbenes.
abstract: Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal 1,3-insertion into N-H and O-H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bisfunctionalized (Z)-olefins with perfect regio- and stereoselectivity. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition-metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles.
authors.affiliation: Department of Chemistry, The Scripps Research Institute , 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
authors.forename: Stepan
authors.initials: S
authors.lastname: Chuprakov
authors.forename: Brady T
authors.initials: BT
authors.lastname: Worrell
authors.forename: Nicklas
authors.initials: N
authors.lastname: Selander
authors.forename: Rakesh K
authors.initials: RK
authors.lastname: Sit
authors.forename: Valery V
authors.initials: VV
authors.lastname: Fokin
mesh_terms: D000577:Amides / Q000737:chemistry; D001372:Aza Compounds / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry; D002384:Catalysis; D018360:Crystallography, X-Ray; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D000577:Amides; D001372:Aza Compounds; D002264:Carboxylic Acids; D014753:Vinyl Compounds; C030011:carbene; D012238:Rhodium; D008697:Methane