The reactions of 5-substituted furfurylamines with anhydrides of α,β-unsaturated carboxylic acids (acryloyl chloride and maleic anhydride) were studied. The first step of the reaction mechanism involved acylation of furfurylamine nitrogen atom, followed by a stereospecific, spontaneous intramolecular Diels–Alder reaction at the furan ring of the N-furfurylamide intermediates. When the starting materials were 5-alkyl-substituted furfurylamines, the expected 1-oxo-2,3,7,7a-hexahydro-1H-3a,6-epoxyisoindoles or the corresponding 7-carboxylic acids were obtained in up to 98% yields. The acylation of 5-aryl-substituted furfurylamines with maleic anhydride led to N-furfurylmaleic amides, which formed a dynamic equilibrium in solutions with adducts formed by intramolecular [4+2] cycloaddition, 3a,6-epoxyisoindole-7-carboxylic acids, as proved by NMR spectroscopy. X-ray structural analysis results show that these mixtures crystallized in the form of the cyclic tautomer.
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The work was performed with support from the Russian Foundation for Basic Research, project No. 13-03-00105 and U.S. National Science Foundation (PREMDMR-0934212).
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The Supplementary information file, containing the complete X-ray structural analysis data for compound 6c and NMR spectra copies for tautomeric mixture of compounds 5Ac, 5Bc, 6c, is available online at http://link.springer.com/journal/10593.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, 2016, 52(4), 225–236
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Zubkov, F.I., Golubev, V.D., Zaytsev, V.P. et al. Ring-chain tautomerism in the products of the reaction between 5-substituted furfurylamines and anhydrides of α,β-unsaturated carboxylic acids. Chem Heterocycl Comp 52, 225–236 (2016). https://doi.org/10.1007/s10593-016-1868-9
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DOI: https://doi.org/10.1007/s10593-016-1868-9