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For recent examples of secondary nucleophiles in Pd catalysis
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Sandrock, D. L.; Jean-Gerard, L.; Chen, C.-Y.; Dreher, S. D.; Molander, G. A. J. Am. Chem. Soc. 2010, 132, 17108 For recent examples of secondary nucleophiles in Ni catalysis: Melzig, L.; Gavryushin, A.; Knochel, P. Org. Lett. 2007, 9, 5529
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While a Ni(0)-Ni(II) catalytic cycle cannot be conclusively ruled out, we favor a Ni(I)-Ni(III) catalytic cycle for such Ni-catalyzed reactions. See
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While a Ni(0)-Ni(II) catalytic cycle cannot be conclusively ruled out, we favor a Ni(I)-Ni(III) catalytic cycle for such Ni-catalyzed reactions. See: Phapale, V. B.; Guisan-Ceinos, M.; Bunuel, E.; Cardenas, D. J. Chem.-Eur. J. 2009, 15, 12681
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34250863375
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For a Cu-catalyzed cross-coupling reaction involving t -BuMgCl and primary alkyl halides, see
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For a Cu-catalyzed cross-coupling reaction involving t -BuMgCl and primary alkyl halides, see: Terao, J.; Todo, H.; Begum, S. A.; Kuniyasu, H.; Kambe, N. Angew. Chem., Int. Ed. 2007, 46, 2086
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79957990572
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While this paper was under review, a separate Ni/NHC-catalyzed process for the cross-coupling of tertiary alkylmagnesium halides and aryl bromides was published:, not supplied.
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Lohre, C.; Droge, T.; Wang, C.; Glorius, F. While this paper was under review, a separate Ni/NHC-catalyzed process for the cross-coupling of tertiary alkylmagnesium halides and aryl bromides was published: Chem.-Eur. J. 2011, not supplied.
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57549115030
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For reviews of NHC ligands in cross-coupling reactions, see
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For reviews of NHC ligands in cross-coupling reactions, see: Marion, N.; Nolan, S. Acc. Chem. Res. 2008, 41, 1440
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34250821753
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While the exact role of water in this system remains unclear, there is precedent for a similarly important water effect with Ni-catalyzed Hiyama cross-coupling reactions in:;;, Additionally, the importance of water in the activation of Pd(II) salts has been previously demonstrated. See:;; Chem. Lett. 1992, 2177
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While the exact role of water in this system remains unclear, there is precedent for a similarly important water effect with Ni-catalyzed Hiyama cross-coupling reactions in: Strotman, N. A.; Sommer, S.; Fu, G. C. Angew. Chem., Int. Ed. 2007, 46, 3556 Additionally, the importance of water in the activation of Pd(II) salts has been previously demonstrated. See: Ozawa, F.; Kubo, A.; Hayaski, T. Chem. Lett. 1992, 2177
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79957997801
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6 with a mortar and pestle and heating the powder under high vacuum in an oil bath at 100 °C for 20 min, then at 120 °C for an additional 5-10 min (see Supporting Information for more details). The powder was rapidly stirred to ensure homogeneous heating. The extent of dehydration can be readily determined by the mass change before/after heating under vacuum.
-
6 with a mortar and pestle and heating the powder under high vacuum in an oil bath at 100 °C for 20 min, then at 120 °C for an additional 5-10 min (see Supporting Information for more details). The powder was rapidly stirred to ensure homogeneous heating. The extent of dehydration can be readily determined by the mass change before/after heating under vacuum.
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32
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79958014933
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In contrast to our original report on the Ni-catalyzed Negishi cross-coupling of secondary alkylzinc halides and aryl iodides with terpyridine as the ligand (ref 3k), the addition of LiCl (1 equiv) does not inhibit catalytic turnover or promote isomerization of the nucleophile.
-
In contrast to our original report on the Ni-catalyzed Negishi cross-coupling of secondary alkylzinc halides and aryl iodides with terpyridine as the ligand (ref 3k), the addition of LiCl (1 equiv) does not inhibit catalytic turnover or promote isomerization of the nucleophile.
-
-
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33
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79957971597
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The failure of NaO t -Bu to facilitate the reaction suggests that kinetically slow in situ deprotonation of the NHC by the Grignard reagent is not responsible for the failure of the anhydrous reactions.
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The failure of NaO t -Bu to facilitate the reaction suggests that kinetically slow in situ deprotonation of the NHC by the Grignard reagent is not responsible for the failure of the anhydrous reactions.
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-
-
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34
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79958007872
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Use of the vinyl bromide resulted in the formation of more reduction product than with use of the vinyl chloride.
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Use of the vinyl bromide resulted in the formation of more reduction product than with use of the vinyl chloride.
-
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35
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0001547002
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Examples of the Ni-catalyzed cross-coupling of trans -β-bromostyrene and t -BuMgCl have been previously reported in
-
Examples of the Ni-catalyzed cross-coupling of trans -β-bromostyrene and t -BuMgCl have been previously reported in: Hayashi, T.; Konishi, M.; Yokota, K.; Kumada, M. Chem. Lett. 1980, 767
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Hayashi, T.1
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Kumada, M.4
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