Optimization of synthesis of (S)-omeprazole catalyzed by soybean pod
peroxidase in water-in-oil microemulsions using RSM
Abstract
Response surface methodology (RSM) was used to optimize the oxidizing
the omeprazole sulfide to (S)-omeprazole catalyzed by environmentally
friendly catalyst soybean pod peroxidase (SPP) in cetyltrimethylammonium
bromide (CTAB)/isooctane/n-butyl alcohol/water water-in-oil
microemulsions. With the initial concentration of SPP of 3200 U ml-1,
the conversion of the omeprazole sulfide, the (S)-omeprazole yield and
ee were 93.75%, 91.56% and 96.08%, respectively, under the optimal
conditions: Wo of 15.85, the concentration of H2O2 of 22.44 mM and
reaction temperature of 49.68 °C, respectively. The proposed mechanism
of asymmetric sulfoxidations catalyzed by SPP involves three concomitant
mechanisms as follows: (1) a two-electron reduction of SPP-I, (2) a
single-electron transfer to SPP-I and (3) nonenzymatic reactions,
including five enzymatic and two nonenzymatic reactions, which is
reasonable and can express the oxidations. With 5.44% of the average
relative error, a kinetic model based on the mechanisms fitting observed
data very well was established, and the SPP-catalyzed reactions
including both the two-electron reduction and the single-electron
transfer mechanisms obey ping-pong mechanism with substrate and product
inhibition, while nonenzymatic reactions follow a power law. This study
has also demonstrated the feasibility of SPP as a substitute with low
cost, excellent enantioselectivity and better thermal stability.