| Summary: | Lactonization reactions through hydrolase-catalyzed peracid formation. Use of lipases for chemoenzymatic Baeyer–Villiger oxidations of cyclobutanones. A one-pot chemoenzymatic method has been described for the synthesis of gamma-butyrolactones starting from the corresponding ketones through a Baeyer–Villiger reaction. The approach is based on a lipase-catalyzed perhydrolysis for the formation of peracetic acid, which is the responsible for the ketone oxidation. Optimization studies have been performed in the oxidation of cyclobutanone, finding Candida antarctica lipase type B, ethyl acetate and urea-hydrogen peroxide complex as the best system. The relative ratio of these reagents has also been analyzed in depth. This synthetic approach has been successfully extended to a family of 3-substituted cyclobutanones in high substrate concentration, yielding the corresponding lactones with excellent isolated yields and purities, under mild reaction conditions and after a simple extraction protocol. Ministerio de Ciencia e Innovación (MICINN-12-CTQ2011-24237 y CTQ-2013-44153-P) Principado de Asturias (SV-PA-13-ECOEMP-42) Universidad de Oviedo (UNOV-13-EMERG-01)
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