Premium
Photoenzymatic Reduction of CC Double Bonds
Author(s) -
Grau Maria Mifsud,
van der Toorn John C.,
Otten Linda G.,
Macheroux Peter,
Taglieber Andreas,
Zilly Felipe E.,
Arends Isabel W. C. E.,
Hollmann Frank
Publication year - 2009
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200900560
Subject(s) - chemistry , chemoselectivity , double bond , cofactor , biocatalysis , ketone , aldehyde , conjugated system , combinatorial chemistry , reductase , stereochemistry , enzyme , catalysis , organic chemistry , reaction mechanism , polymer
A simplified procedure for cell‐free biocatalytic reductions of conjugated CC double bonds using old yellow enzymes (OYEs) is reported. Instead of indirectly regenerating YqjM (an OYE homologue from B. subtilis ) or NemA ( N ‐ethylmaleimide reductase from E. coli ) via regeneration of reduced nicotinamide cofactors, we demonstrate that direct regeneration of catalytically active reduced flavins is an efficient and convenient approach. Reducing equivalents are provided from simple sacrificial electron donors such as ethylenediaminetetraacetate (EDTA), formate, or phosphite via photocatalytic oxidation. This novel photoenzymatic reaction scheme was characterized. Up to 65% rates of the NADH‐driven reaction were obtained while preserving enantioselectivity. The chemoselectivity of the novel approach was exclusive. Even when using crude cell extracts as biocatalyst preparations, only CC bond reduction was observed while ketone and aldehyde groups remained unaltered. Overall, a simple and practical approach for photobiocatalytic reductions is presented.