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Recently, a directed ortho-lithiation/transmetalation sequence was used in the preparation of triarylindium reagents. Pena, M. A.; Perez Sestelo, J.; Sarandeses, L. A. J. Org. Chem. 2007, 72, 1271.
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Recently, a directed ortho-lithiation/transmetalation sequence was used in the preparation of triarylindium reagents. Pena, M. A.; Perez Sestelo, J.; Sarandeses, L. A. J. Org. Chem. 2007, 72, 1271.
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Magnesium: c
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Magnesium: (c) Knochel, P.; Dohle, W.; Gommermann, N.; Kniesel, F. F.; Kopp, F.; Korn, T.; Sapountzis, I; Vu, V. A. Angew. Chem., Int. Ed. 2003, 42, 4302.
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(e) Ila, H.; Baron, O.; Wagner, A. J.; Knochel, P. Chem. Lett. 2006, 35, 2.
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German Patent DE 102006015378, In the preparation of this manuscript, we became aware of a manuscript in review J. Am. Chem. Soc, by Knochel and Chen detailing the direct insertion of indium into aryl and heteroaryl iodides and the cross-coupling of the so-formed indium reagents with aryl halide to form biaryls
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Knochel, P.; Gavryushin, A.; Malakhov, V. A. German Patent DE 102006015378, 2007. In the preparation of this manuscript, we became aware of a manuscript in review (J. Am. Chem. Soc.) by Knochel and Chen detailing the direct insertion of indium into aryl and heteroaryl iodides and the cross-coupling of the so-formed indium reagents with aryl halide to form biaryls.
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Indium containing 0.1% Mg was prepared my mixing 102.6 mg of indium metal with 11.4 mg of commercially available indium containing 1% Mg (Aldrich).
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Indium containing 0.1% Mg was prepared my mixing 102.6 mg of indium metal with 11.4 mg of commercially available indium containing 1% Mg (Aldrich).
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For a previous preparation of 3a, see: So, C. M.; Lau, C. P.; Kwong, F. Y. Org. Lett. 2008, 9, 2795.
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Electron-deficient aryl bromides were also suitable partners for the cross-coupling reaction with the in situ formed arylindium reagents, furnishing biaryl products 3 in similar or slightly lower yields when compared to the corresponding aryl iodides. Electron-rich aryl bromides, however, gave very poor yields 5-20, of cross-coupled products
-
Electron-deficient aryl bromides were also suitable partners for the cross-coupling reaction with the in situ formed arylindium reagents, furnishing biaryl products 3 in similar or slightly lower yields when compared to the corresponding aryl iodides. Electron-rich aryl bromides, however, gave very poor yields (5-20%) of cross-coupled products.
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While the indium metal recovered after the insertion reaction (30% of the total used) could be directly reused in insertion and cross-coupling reactions with minimal (< 10, decrease in yield, the indium metal recovered after zinc-mediated reduction of the residual aqueous indium salts (50-60% of the total used) was a softball-like clump that could not be reused directly because of its decreased surface area compared to indium powder. Work on preparing this material for reuse in insertion and cross-coupling reactions is currently in progress
-
While the indium metal recovered after the insertion reaction (30% of the total used) could be directly reused in insertion and cross-coupling reactions with minimal (< 10%) decrease in yield, the indium metal recovered after zinc-mediated reduction of the residual aqueous indium salts (50-60% of the total used) was a softball-like clump that could not be reused directly because of its decreased surface area compared to indium powder. Work on preparing this material for reuse in insertion and cross-coupling reactions is currently in progress.
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