Mn-catalyzed aromatic C-H alkenylation with terminal alkynes.

Beijing National Laboratory of Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

Journal of the American Chemical Society 2013 Jan 30

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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.

Citation

Bingwei Zhou, Hui Chen, Congyang Wang. Mn-catalyzed aromatic C-H alkenylation with terminal alkynes. Journal of the American Chemical Society. 2013 Jan 30;135(4):1264-7