Photo-enzyme catalysis enabled E → Z isomerization of alkenes

[Display omitted] •A high-efficiency photo-enzymatic system with wide substrate range, mild reaction conditions and simple operation for the E to Z isomerization of α, β-unsaturated ester and stilbene has been developed.•The specific natural fold of enzyme and the specific wavelengths of light (410 nm) are both indispensable for this photo-enzyme synergistic catalysis the isomerization of alkene.•The importance of the specific natural fold of enzyme for its catalytic efficiency in this reaction was demonstrated by fluorescence spectroscopy, synchronous fluorescence spectroscopy and circular dichroism. A facile and high efficiency photo-enzyme catalysis system for the E to Z isomerization of alkenes has been developed. Using a photo-enzyme hybrid system with good versatility, 43 Z-configurations of α, β-unsaturated esters and stilbenes were synthesized in good yields, in which the highest Z/E ratio was 91:9. This photo-enzyme catalysis system has wide substrate range, mild reaction conditions and simple operation, and it is in line with atom-economic synthesis.