The CuI-mediated click reaction of aromatic azides, containing the carboxyl moiety in the ortho position to the azido group, with ethyl prop-2-ynyl methylphosphonate proceeded via a concurrent pathway whereby the formation of acrylamides predominated over "classical" cycloaddition products 1,2,3-triazoles. The reaction appears to be specific toward the ortho-carboxyl-substituted aromatic azides, while aryl azides with other substituents do not give the "reduction" products, but form the expected click products: (1-aryl-1H-1,2,3-triazol-4-yl)methyl ethyl methylphosphonates. The reaction mechanism is discussed.
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The authors are grateful to the Ministry of Education and Science of Ukraine for financial support of this work (grant No. 0118U003610).
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Published in Khimiya Geterotsiklicheskikh Soedinenii, 2019, 55(4/5), 374–378
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Pokhodylo, N.T., Shyyka, O.Y., Tupychak, M.A. et al. Concurrent pathway and unexpected products in the CuAAC reaction of ethyl prop-2-ynyl methylphosphonate with aromatic azides. Chem Heterocycl Comp 55, 374–378 (2019). https://doi.org/10.1007/s10593-019-02467-9
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DOI: https://doi.org/10.1007/s10593-019-02467-9