Engineered P450pyr monooxygenase for asymmetric epoxidation of alkenes with unique and high enantioselectivityElectronic supplementary information (ESI) available: Experimental details, molecular modeling, HPLC chromatograms, and 1H NMR spectra. See DOI: 10.1039/c3cc46675b

A triple mutant of P450pyr monooxygenase (P450pyrTM) catalysed the epoxidation of several para -substituted styrenes as the first enzyme showing high ( R )-enantioselectivity and high conversion, demonstrated a broad substrate range, and showed high enantioselectivity for the epoxidation of an unconjugated 1,1-disubstituted alkene, 2-methyl-3-phenyl-1-propene, and a cyclic alkene, N -phenoxycarbonyl-1,2,5,6-tetrahydropyridine, respectively. P450pyrTM monooxygenase demonstrated unique and excellent ( R )-enantioselectivity for the epoxidation of para -substituted styrenes and high enantioselectivity for several other epoxidations.