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Volumn 350, Issue 10, 2008, Pages 1484-1488

Cobalt-catalyzed cross-coupling reaction between functionalized primary and secondary alkyl halides and aliphatic Grignard reagents

Author keywords

Aliphatic Grignard reagents; Alkyl alkyl; Cobalt catalyzed reaction; Cross coupling; Secondary alkyl bromides

Indexed keywords


EID: 53849091310     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/adsc.200800166     Document Type: Article
Times cited : (84)

References (74)
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    • The yields of cross-coupling products are generally higher from cycloalkyl halides than from acyclic secondary alkyl halides. It is reasonable to consider that the oxidative addition is easier from cyclic secondary alkyl halides since this reaction is very sensitive to steric hindrance as demonstrated recently by Fu: I. D. Hills, M. R. Netherton, G. C. Fu, Angew. Chem. 2003, 115, 5927;
    • The yields of cross-coupling products are generally higher from cycloalkyl halides than from acyclic secondary alkyl halides. It is reasonable to consider that the oxidative addition is easier from cyclic secondary alkyl halides since this reaction is very sensitive to steric hindrance as demonstrated recently by Fu: I. D. Hills, M. R. Netherton, G. C. Fu, Angew. Chem. 2003, 115, 5927;
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    • Oshima recently reported the cross-coupling reaction between alkyl halides and allylic or benzylic Grignard reagents: H. Ohmiya, T. Tsuji, H. Yorimitsu, K. Oshima, Chem. Eur. J. 2004, 10, 5640;
    • a) Oshima recently reported the cross-coupling reaction between alkyl halides and allylic or benzylic Grignard reagents: H. Ohmiya, T. Tsuji, H. Yorimitsu, K. Oshima, Chem. Eur. J. 2004, 10, 5640;
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    • it should be noted that the reactivity of these Grignard reagents is quite different from that of non activated alkylmagnesium reagents used in the procedure described above; b Oshima made a substantial contribution to the development of cobalt-catalyzed reactions; for a recent review see: H. Yorimitsu, K. Oshima, Pure Appl. Chem. 2007, 78, 441
    • it should be noted that the reactivity of these Grignard reagents is quite different from that of non activated alkylmagnesium reagents used in the procedure described above; b) Oshima made a substantial contribution to the development of cobalt-catalyzed reactions; for a recent review see: H. Yorimitsu, K. Oshima, Pure Appl. Chem. 2007, 78, 441.
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    • A report on the coupling of primary alkyl bromides with primary alkyl-Grignard reagents under iron catalysis was recently published: K. G. Dongol, H. Koh, M. Sau, C. L. L. Chai, Adv. Synth. Catal. 2007, 349, 1015; the reaction is performed in the presence of 3 mol% Fe(OAc)2-Xantphos (1:2) in diethyl ether at room temperature. Yields are moderate (46-64, in addition, the use of cyclic secondary alkyl bromides resulted in poor yields 8-43, and no example of an acyclic secondary alkyl bromide was described
    • 2-Xantphos (1:2) in diethyl ether at room temperature. Yields are moderate (46-64%), in addition, the use of cyclic secondary alkyl bromides resulted in poor yields (8-43%) and no example of an acyclic secondary alkyl bromide was described.
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    • [4d,e]
    • [4d,e]
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    • We have verified that bromine-iodine exchange is very slow under our conditions. Thus, by stirring our catalytic system (CoCl2·2 LiI, 4TMEDA) with 2-bromooctane ratio LiI/s-OctBr, 1:1, only 4% of 2-iodobutane were detected after 16 h at room temperature
    • 2·2 LiI, 4TMEDA) with 2-bromooctane (ratio LiI/s-OctBr = 1:1), only 4% of 2-iodobutane were detected after 16 h at room temperature.


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