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Asymmetric synthesis of trans-4,5-dioxygenated cyclopentenone derivatives by organocatalyzed rearrangement of pyranones and enzymatic dynamic kinetic resolution |
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| Authors: | João PM NunesLuís F Veiros Pedro D VazCarlos AM Afonso Stephen Caddick |
| Institution: | a CQFM, Centro de Química-Física Molecular, IN—Institute of Nanosciences and Nanotechnology, Instituto Superior Técnico, 1049-001 Lisboa, Portugal b CQE, Centro de Química Estrutural, Instituto Superior Técnico,1049-001 Lisboa, Portugal c CQB, Centro de Química e Bioquímica, Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade de Lisboa, C8, Campo Grande, 1749-016 Lisboa, Portugal d iMed.UL, Faculdade de Farmácia da Universidade de Lisboa Av. Prof. Gama Pinto, 1649-003 Lisboa, Portugal e Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK |
| Abstract: | Dioxygenated cyclopentenones are versatile building blocks for the synthesis of several natural products. Herein we report a direct asymmetric synthesis of trans-4,5-dioxygenated cyclopentenone derivatives through base-catalyzed rearrangement of pyranones followed by dynamic kinetic resolution. Milder conditions than previously reported for this rearrangement have been found regarding amine base catalysis, solvent and temperature effects. All data supports a mechanism involving cyclization of an intermediate formed by electrocyclic ring opening of a pyranone-derived enol. We have developed conditions for asymmetric synthesis of trans-4-tert-butoxy-5-hydroxycyclopent-2-enone, in 81% yield and 95% ee, and analogous dioxygenated cyclopentenones, via a lipase induced dynamic kinetic resolution. |
| Keywords: | Organocatalysis Dynamic kinetic resolution Lipase-catalyzed acylation Pyranone rearrangement trans-Dioxygenated cyclopentenone |
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