Biocatalytic Access to Chiral Polyesters by an Artificial Enzyme Cascade Synthesis. Issue 23 (22nd September 2015)

• Record Type: Journal Article
• Authors: Schmidt, Sandy; Büchsenschütz, Hanna C.; Scherkus, Christian; Liese, Andreas; Gröger, Harald; Bornscheuer, Uwe T.
• Is Part Of: ChemCatChem. Volume 7:Issue 23(2015:Dec.)
• Page Start: 3951
• Page End: 3955
• Publication Date: 2015-09-22
• Subjects: alcohols -- enzyme catalysis -- dehydrogenation -- enantioselectivity -- polymerization; Catalysis -- Periodicals; 541.39505
• DOI: 10.1002/cctc.201500823
• Languages: English
• ISSNs: 1867-3880

Abstract

Abstract: Chiral polyesters in general can be employed for versatile biomedical purposes, but in vitro enzyme catalyzed biocatalytic routes by a multiple‐step cascade to make these functional biodegradable chiral polyesters have been hardly investigated. Recently, we developed an artificial three‐step enzymatic cascade synthesis by combining an alcohol dehydrogenase (ADH), a Baeyer–Villiger monooxygenase (BVMO) and a lipase (CAL‐A). Here, we extended this cascade for the synthesis of chiral methyl‐substituted oligo‐ɛ‐caprolactone derivatives to achieve both, the generation of chirality in a monomer and the subsequent polymerization. Several substrates were examined and provided access to functionalized chiral compounds in high yields (up to >99 %) and optical purities (up to >99 % ee). By subsequent enzymatic enantioselective ring opening of the enantiopure monomers, oligomeric lactones were successfully synthesized. Abstract : Rotate me ! By combining three enzymes (LK‐ADH, CHMO, CAL‐A), which are evolutionary not connected, to an artificial cascade, optically active chiral oligomers can be synthesized from nonchiral or racemic methyl‐substituted cyclohexanol derivatives.