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Cobalt-catalyzed Selective C--F Bond Activation and Alkylation of Polyfluoroaryl Imines

Cobalt-catalyzed Selective C--F Bond Activation and Alkylation of Polyfluoroaryl Imines
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摘要 In this paper the C--F bond activation of polyfluoroaryl imines is explored at cobalt(0) center with an imine-N atom as an anchoring group. The reaction of F5C6-CH=N-(2'-ClC6H4) (2) and FsC6-CH=N-C6H5 (3) with Co(PMe3h afforded the C-F bond activation products (ortho-F4C6-CH=N-(2'-CIC6H4))Co(I)(PMe3)3 (5) and (ortho-F4C6-CH=N-C6Hs)Co(II)(F)(PMe3)2 (6), while only n-(C=N) coordinated cobalt(0) complex (2,4,5- F3C6H2-CH=N-(4'-ClC6H4))Co(0)(PMe3)3 (4) was obtained from 2,4,5-F3C6H2-CH=N-(4'-C1C6H4) (1) without C--F bond activation. Complexes 4--6 were characterized through X-ray single crystal diffraction. It was also found that dialkylation of N-(perfluorobenzylidene)benzenamine with organozinc reagents could be catalyzed by Co(PMe3)4 via C,C-coupling reaction under mild conditions. In this paper the C--F bond activation of polyfluoroaryl imines is explored at cobalt(0) center with an imine-N atom as an anchoring group. The reaction of F5C6-CH=N-(2'-ClC6H4) (2) and FsC6-CH=N-C6H5 (3) with Co(PMe3h afforded the C-F bond activation products (ortho-F4C6-CH=N-(2'-CIC6H4))Co(I)(PMe3)3 (5) and (ortho-F4C6-CH=N-C6Hs)Co(II)(F)(PMe3)2 (6), while only n-(C=N) coordinated cobalt(0) complex (2,4,5- F3C6H2-CH=N-(4'-ClC6H4))Co(0)(PMe3)3 (4) was obtained from 2,4,5-F3C6H2-CH=N-(4'-C1C6H4) (1) without C--F bond activation. Complexes 4--6 were characterized through X-ray single crystal diffraction. It was also found that dialkylation of N-(perfluorobenzylidene)benzenamine with organozinc reagents could be catalyzed by Co(PMe3)4 via C,C-coupling reaction under mild conditions.
出处 《Chinese Journal of Chemistry》 SCIE CAS CSCD 2013年第7期927-932,共6页 中国化学(英文版)
基金 Acknowledgement We gratefully acknowledge the support by National Natural Science Foundation of China (No. 21172132). We also thank the kind assistance from Prof. Dieter Fenske and Dr. Olaf Fuhr (Karlsruhe Nano-Micro Facility, KNMF) for the X-ray diffraction analysis.
关键词 C--F bond activation COBALT IMINE organozinc reagent C C-coupling C--F bond activation, cobalt, imine, organozinc reagent, C,C-coupling
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