Bioreduction of alpha-methylcinnamaldehyde derivatives: chemo-enzymatic asymmetric synthesis of Lilial and Helional

Dalton Trans. 2010 Sep 28;39(36):8472-6. doi: 10.1039/c002971h. Epub 2010 May 11.

Abstract

Nonracemic aryl-substituted alpha-methyldihydrocinnamaldehyde derivatives employed as olfactory principles in perfumes (Lilial, Helional) were obtained via enzymatic reduction of the corresponding cinnamaldehyde precursors using cloned and overexpressed ene-reductases. (R)-Enantiomers were obtained using the old-yellow-enzyme (OYE) homolog YqjM from Bacillus subtilis and 12-oxophytodienoic acid reductase isoenzyme OPR1 from tomato (e.e.(max) 53%), and (S)-aldehydes were furnished in up to 97% e.e. using isoenzyme OPR3, nicotinamide 2-cyclohexene-1-one reductase NCR from Zymomonas mobilis and yeast OYE isoenzymes 1-3 under optimised reaction conditions in the presence of t-butyl methyl ether as the co-solvent. The stereochemical outcome of the reduction of alpha-methylcinnamaldehyde using NCR and OYEs 1-3 [previously reported to be (R)] was unambiguously corrected to be (S).

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acrolein / analogs & derivatives*
  • Acrolein / chemistry
  • Aldehydes / chemistry
  • Aldehydes / metabolism*
  • Bacillus subtilis / enzymology
  • Bacterial Proteins / metabolism
  • Binding Sites
  • Biocatalysis
  • Enzymes / metabolism*
  • Fungal Proteins / metabolism
  • Models, Molecular
  • NADPH Dehydrogenase / metabolism
  • Oxidation-Reduction
  • Oxidoreductases / metabolism
  • Oxidoreductases Acting on CH-CH Group Donors / metabolism
  • Perfume / chemistry
  • Perfume / metabolism*
  • Plant Proteins / metabolism
  • Solanum lycopersicum / enzymology
  • Stereoisomerism
  • Zymomonas / enzymology

Substances

  • Aldehydes
  • Bacterial Proteins
  • Enzymes
  • Fungal Proteins
  • Perfume
  • Plant Proteins
  • Acrolein
  • Oxidoreductases
  • Oxidoreductases Acting on CH-CH Group Donors
  • 2-cyclohexen-1-one reductase (NAD(P)H)
  • 12-oxophytodienoate reductase
  • NADPH Dehydrogenase
  • cinnamaldehyde
  • lilial