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J Am Chem Soc. 2013 Jan 30;135(4):1264-7. doi: 10.1021/ja311689k. Epub 2013 Jan 15.

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

Author information

1
Beijing National Laboratory of Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

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.

PMID:
23286776
DOI:
10.1021/ja311689k
[Indexed for MEDLINE]

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