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In our original article ref 1, we noted a weak inhibitory property of benzyl azide. We have subsequently found that commercial benzyl azide frequently contains an unidentified trace impurity that either inhibits the CuAAC reaction or poisons the copper catalyst. No inhibitory effect was observed when carefully distilled benzyl azide was employed, and therefore our prior report is in error in this respect. Such distilled material was used in all experiments described in these articles
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In our original article (ref 1), we noted a weak inhibitory property of benzyl azide. We have subsequently found that commercial benzyl azide frequently contains an unidentified trace impurity that either inhibits the CuAAC reaction or poisons the copper catalyst. No inhibitory effect was observed when carefully distilled benzyl azide was employed, and therefore our prior report is in error in this respect. Such distilled material was used in all experiments described in these articles.
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We have observed that certain minor products of the photochemical decomposition of aromatic azides in DMSO act as potent accelerating ligands for CuAAC reactions of other aromatic azides, increasing rates by several orders of magnitude and producing unprecedented amounts of 1,5-triazoles for a copper-mediated process. These phenomena are currently being investigated and will be described in detail elsewhere. The catalytic photoproducts do not form in the presence of tert-butanol
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We have observed that certain minor products of the photochemical decomposition of aromatic azides in DMSO act as potent accelerating ligands for CuAAC reactions of other aromatic azides, increasing rates by several orders of magnitude and producing unprecedented amounts of 1,5-triazoles for a copper-mediated process. These phenomena are currently being investigated and will be described in detail elsewhere. The catalytic photoproducts do not form in the presence of tert-butanol.
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An example of a Cu·C(triazole) intermediate obtained from a CuAAC reaction has been recently characterized by X-ray crystallography: Nolte, C.; Mayer, P.; Straub, B. F. Angew. Chem., Int. Ed. 2007, 46, 2101-2103.
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1A) in our parlance, with the pendant carboxylate arm serving a coordinating role: Su, C.-Y.; Yang, X.-P.; Kang, B.-S.; Mak, T. C. W. Angew. Chem., Int. Ed. 2001, 40, 1725-1728.
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1A) in our parlance, with the pendant carboxylate arm serving a coordinating role: Su, C.-Y.; Yang, X.-P.; Kang, B.-S.; Mak, T. C. W. Angew. Chem., Int. Ed. 2001, 40, 1725-1728.
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A similar situation of interconverting catalysts giving rise to unusual rate profiles was sorted out nicely in Nielsen, L. P. C, Stevenson, C. P, Blackmond, D. G, Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 1360-1362
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A similar situation of interconverting catalysts giving rise to unusual rate profiles was sorted out nicely in Nielsen, L. P. C.; Stevenson, C. P.; Blackmond, D. G.; Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 1360-1362.
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