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Soon after the submission of this article, a report on ligandless copper-catalyzed coupling of aryl bromides and chlorides with ammonia in water was published Xu, H. Wolf, C. Chem. Commun. 2009, 3035-3037. In our hands, the reaction of 2-bromotoluene with aqueous ammonia by the published protocols using various sources of copper iodide, open or closed vessels, and reaction vessels with varying headspaces afforded less than 10% of ortho-toluidine. Thus, we abandonded studies to compare our system to this one.
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While this work was under review, Ma and co-workers reported the coupling of 2-bromoanisole and 2-bromotoluene with ammonia in water in the presence of 20% CuI and 40 mol % of 4-hydroxy-Lproline to give 81 and 55% yields of the primary arylamines, respectively: Jiang, L.; Lu, X.; Zhang, H.; Jiang, Y.; Ma, D. J. Org. Chem. 2009, 74, 4542-4546. In contrast to the work with ligandless catalysts in ref 25, we have obtained yields (69 and 60%, respectively) that are close to those published, but these yields are still lower than those in the current work with palladium catalysts.
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