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The only differences between the conditions reported in ref 25 and those reported herein are the catalyst loading (5% vs 10, and the choice of base (K2CO3 vs K3PO4, In addition, we initially encountered some problems with irreproducibility, which were found to be dependant upon maintaining efficient stirring during the course of the reaction, and upon the morphology of the K3PO4 base. Reactions were found to be reproducible only when conducted using K 3PO4 from a new bottle, which was free-flowing, fine granular material Fluka, catalog no. 04347, The importance of K 3PO4 morphology in copper-catalyzed N-arylation reactions has previously been observed by Buchwald and co-workers; see: Klapars, A, Huang, X, Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 7421-7428
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4 morphology in copper-catalyzed N-arylation reactions has previously been observed by Buchwald and co-workers; see: Klapars, A.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 7421-7428.
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In an attempt to overcome this limitation for the poor control of regioselectivity and expand the scope of available substrates, we also evaluated the use of, o-bromo and iodoaryl triflates, which are readily synthesized by ortho-halogenation and triflation of phenols. Unfortunately only trace amounts (≤5, of the desired products were obtained, presumably because unlike Pd-catalyzed transformations, Cu does not undergo effective oxidative addition to the aryl triflate bond. The trace amounts of benzoxazole observed in these reactions may be due to a background reaction pathway not involving cross-coupling e.g, triflate hydrolysis followed by dehydrative annulation or nucleophilic aromatic substitution
-
In an attempt to overcome this limitation for the poor control of regioselectivity and expand the scope of available substrates, we also evaluated the use of, o-bromo and iodoaryl triflates, which are readily synthesized by ortho-halogenation and triflation of phenols. Unfortunately only trace amounts (≤5%) of the desired products were obtained, presumably because unlike Pd-catalyzed transformations, Cu does not undergo effective oxidative addition to the aryl triflate bond. The trace amounts of benzoxazole observed in these reactions may be due to a background reaction pathway not involving cross-coupling (e.g., triflate hydrolysis followed by dehydrative annulation or nucleophilic aromatic substitution).
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