title: Mn-catalyzed aromatic C-H alkenylation with terminal alkynes.
abstract: The first manganese-catalyzed aromatic C-H alkenylation with terminal alkynes is described. The procedure features an operationally simple catalyst system containing commercially available MnBr(CO)(5) and dicyclohexylamine (Cy(2)NH). The reaction occurs readily in a highly chemo-, regio-, and stereoselective manner delivering anti-Markovnikov E-configured olefins in high yields. Experimental study and DFT calculations reveal that (1) the reaction is initiated by a C-H activation step via the cooperation of manganese and base; (2) manganacycle and alkynylmanganese species are the key reaction intermediates; and (3) the ligand-to-ligand H-transfer and alkynyl-assisted C-H activation are the key steps rendering the reaction catalytic in manganese.
authors.affiliation: Beijing National Laboratory of Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
authors.forename: Bingwei
authors.initials: B
authors.lastname: Zhou
authors.forename: Hui
authors.initials: H
authors.lastname: Chen
authors.forename: Congyang
authors.initials: C
authors.lastname: Wang
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D008345:Manganese / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*
chemical_list: D000475:Alkenes; D000480:Alkynes; D009942:Organometallic Compounds; D008345:Manganese