Baeyer-Villiger monooxygenase-catalyzed desymmetrizations of cyclobutanones. Application to the synthesis of valuable spirolactones

[摘要] A series of gamma-butyrolactone derivatives, including some spiranic ones, was obtained through de-symmetrization of the corresponding prochiral 3-substituted cyclobutanones via Baeyer-Villiger monooxygenase (BVMO)-catalyzed oxidation. After reaction optimization using several commercial enzymes, both antipodes of various lactones were synthesized in most cases with >90% conversion and >80% enantiomeric excess under mild reaction conditions. In some cases alcohol formation was also observed (up to 40% conversion) as an undesired side reaction due to the presence of alcohol dehydrogenases in these preparations. Selected transformations were achieved on a 100 mg scale showing the possibilities of these oxidative biocatalysts as a new source of highly interesting compounds. (C) 2015 Elsevier Ltd. All rights reserved.

[发布日期] 2016-11-17

[效力级别]  Proceedings Paper

[关键词] Asymmetric synthesis;Baeyer-Villiger oxidation;Lactones;Oxygenases;Spiro compounds