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for a review on copper-catalyzed reactions of Grignard reagents, see: c) E. Erdik, Tetrahedron 1984, 40, 641.
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for palladium-catalyzed cross-coupling of primary alkyl halides, see: c
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for palladium-catalyzed cross-coupling of primary alkyl halides, see: c) T. Ishiyama, S. Abe, N. Miyaura, A. Suzuki, Chem. Lett. 1992, 691;
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for nickel-catalyzed cross-coupling of primary alkyl halides see: c
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50
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53849092771
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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;
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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;
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0348134860
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moreover, the intermediate cycloalkylmetals are generally more stable than the secondary acyclic alkylmetals since the β-hydrogen elimination, which requires the complexation of a β-hydrogen atom to the metal, is more difficult
-
Angew. Chem. Int. Ed. 2003, 42, 5749; moreover, the intermediate cycloalkylmetals are generally more stable than the secondary acyclic alkylmetals since the β-hydrogen elimination, which requires the complexation of a β-hydrogen atom to the metal, is more difficult.
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52
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For reviews of the use of alkyl halides in metal catalyzed reactions, see: a
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For reviews of the use of alkyl halides in metal catalyzed reactions, see: a) T.-Y. Luh, M.-k. Leung, K.-T. Wong, Chem. Rev. 2000, 100, 3187;
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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;
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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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58
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33644540458
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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
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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.
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G. Cahiez, V. Habiak, C. Duplais, A. Moyeux, Angew. Chem. 2007, 119, 4442;
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61
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3/TMEDA/HMTA has also been used for the coupling of secondary alkyl halides with alkenyl Grignard reagents: G. Cahiez, C. Duplais, A. Moyeux, Org. Lett. 2007, 9, 3253.
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3/TMEDA/HMTA has also been used for the coupling of secondary alkyl halides with alkenyl Grignard reagents: G. Cahiez, C. Duplais, A. Moyeux, Org. Lett. 2007, 9, 3253.
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For recent reports on iron-catalyzed cross-coupling reactions: a
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For recent reports on iron-catalyzed cross-coupling reactions: a) T. Nagano, T. Hayashi, Org. Lett. 2004, 6, 1297;
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for a recent report on a cobalt-catalyzed cross-coupling reaction
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g) for a recent report on a cobalt-catalyzed cross-coupling reaction: H. Ohmiya, H. Yorimitsu, K. Oshima, J. Am. Chem. Soc. 2006, 128, 1886.
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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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71
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2·2 LiCl: M. Tamura, J. Kochi, Synthesis 1971, 303;
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2·2 LiCl: M. Tamura, J. Kochi, Synthesis 1971, 303;
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0026683208
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[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
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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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