Schmidt, SandySandySchmidtScherkus, ChristianChristianScherkusMuschiol, JanJanMuschiolMenyes, UlfUlfMenyesWinkler, TillTillWinklerHummel, WernerWernerHummelGröger, HaraldHaraldGrögerLiese, AndreasAndreasLieseHerz, Hans GeorgHans GeorgHerzBornscheuer, Uwe TheoUwe TheoBornscheuer2021-08-172021-08-172015-01-19Angewandte Chemie - International Edition 54 (9): 2784-2787 (2015-02-23)http://hdl.handle.net/11420/10104Poly-ε-caprolactone (PCL) is chemically produced on an industrial scale in spite of the need for hazardous peracetic acid as an oxidation reagent. Although Baeyer-Villiger monooxygenases (BVMO) in principle enable the enzymatic synthesis of ε-caprolactone (ε-CL) directly from cyclohexanone with molecular oxygen, current systems suffer from low productivity and are subject to substrate and product inhibition. The major limitations for such a biocatalytic route to produce this bulk chemical were overcome by combining an alcohol dehydrogenase with a BVMO to enable the efficient oxidation of cyclohexanol to ε-CL. Key to success was a subsequent direct ring-opening oligomerization of in situ formed ε-CL in the aqueous phase by using lipase A from Candida antarctica, thus efficiently solving the product inhibition problem and leading to the formation of oligo-ε-CL at more than 20 g L-1 when starting from 200 mM cyclohexanol. This oligomer is easily chemically polymerized to PCL.en1521-37732015927842787Wiley-VCHBaeyer-Villiger monooxygenasesCascade reactionsEnzyme catalysisPolymer synthesisε-caprolactoneChemieTechnikJournal Article10.1002/anie.20141063325597635Journal Article