Biocatalytic Access to Chiral Polyesters by an Artificial Enzyme Cascade Synthesis

Sandy Schmidt, Hanna C. Büchsenschütz, Christian Scherkus, Andreas Liese, Harald Gröger, Uwe T. Bornscheuer

Research output: Contribution to journalArticleResearchpeer-review

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-ε-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. 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.

Original languageEnglish
Pages (from-to)3951-3955
Number of pages5
JournalChemCatChem
Volume7
Issue number23
DOIs
Publication statusPublished - 1 Dec 2015

Fingerprint

Polyesters
Alcohol Dehydrogenase
polyesters
enzymes
cascades
Alcohols
Enzymes
Monomers
Cyclohexanols
Derivatives
dehydrogenases
Chirality
Lipases
Lactones
synthesis
Mixed Function Oxygenases
Lipase
Oligomers
alcohols
monomers

Keywords

  • alcohols
  • dehydrogenation
  • enantioselectivity
  • enzyme catalysis
  • polymerization

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Biocatalytic Access to Chiral Polyesters by an Artificial Enzyme Cascade Synthesis. / Schmidt, Sandy; Büchsenschütz, Hanna C.; Scherkus, Christian; Liese, Andreas; Gröger, Harald; Bornscheuer, Uwe T.

In: ChemCatChem, Vol. 7, No. 23, 01.12.2015, p. 3951-3955.

Research output: Contribution to journalArticleResearchpeer-review

Schmidt, Sandy ; Büchsenschütz, Hanna C. ; Scherkus, Christian ; Liese, Andreas ; Gröger, Harald ; Bornscheuer, Uwe T. / Biocatalytic Access to Chiral Polyesters by an Artificial Enzyme Cascade Synthesis. In: ChemCatChem. 2015 ; Vol. 7, No. 23. pp. 3951-3955.
@article{06b622f2615b49edb02f21938f34647d,
title = "Biocatalytic Access to Chiral Polyesters by an Artificial Enzyme Cascade Synthesis",
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-ε-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. 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.",
keywords = "alcohols, dehydrogenation, enantioselectivity, enzyme catalysis, polymerization",
author = "Sandy Schmidt and B{\"u}chsensch{\"u}tz, {Hanna C.} and Christian Scherkus and Andreas Liese and Harald Gr{\"o}ger and Bornscheuer, {Uwe T.}",
year = "2015",
month = "12",
day = "1",
doi = "10.1002/cctc.201500823",
language = "English",
volume = "7",
pages = "3951--3955",
journal = "ChemCatChem",
issn = "1867-3880",
publisher = "Wiley-VCH",
number = "23",

}

TY - JOUR

T1 - Biocatalytic Access to Chiral Polyesters by an Artificial Enzyme Cascade Synthesis

AU - Schmidt, Sandy

AU - Büchsenschütz, Hanna C.

AU - Scherkus, Christian

AU - Liese, Andreas

AU - Gröger, Harald

AU - Bornscheuer, Uwe T.

PY - 2015/12/1

Y1 - 2015/12/1

N2 - 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-ε-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. 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.

AB - 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-ε-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. 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.

KW - alcohols

KW - dehydrogenation

KW - enantioselectivity

KW - enzyme catalysis

KW - polymerization

UR - http://www.scopus.com/inward/record.url?scp=84954309003&partnerID=8YFLogxK

U2 - 10.1002/cctc.201500823

DO - 10.1002/cctc.201500823

M3 - Article

VL - 7

SP - 3951

EP - 3955

JO - ChemCatChem

JF - ChemCatChem

SN - 1867-3880

IS - 23

ER -