119141-88-7Relevant articles and documents
Synthesis of Esomeprazole and Related Proton Pump Inhibitors through Iron-Catalyzed Enantioselective Sulfoxidation
Nishiguchi, Shigenobu,Izumi, Takuhiro,Kouno, Takayoshi,Sukegawa, Junpei,Ilies, Laurean,Nakamura, Eiichi
, p. 9738 - 9743 (2018)
We report here an application of iron catalysis for the kilogram scale asymmetric synthesis of a proton pump inhibitor, esomeprazole, in 87% yield and 99.4% ee by catalytic sulfoxidation with hydrogen peroxide using an iron salt/chiral Schiff base in combination with a carboxylate salt. Under similar reaction conditions, other proton pump inhibitors such as (S)-lansoprazole, (S)-rabeprazole, and (S)-pantoprazole, were also synthesized in high yield and ee. A carboxylate additive was crucial for the success of this reaction, and we consider that it coordinates to the active iron species, and it also acts as a hydrogen-bond acceptor to coordinate to the substrate through the imidazole NH.
Ti-Salan catalyzed asymmetric sulfoxidation of pyridylmethylthiobenzimidazoles to optically pure proton pump inhibitors
Talsi, Evgenii P.,Bryliakov, Konstantin P.
, p. 84 - 89 (2017)
The asymmetric sulfoxidation of two pyridylmethylthiobenzimidazoles to anti-ulcer drugs of the PPI family (S)-omeprazole and (R)-lansoprazole with hydrogen peroxide, mediated by a series of chiral titanium(IV) salan complexes is reported. High sulfoxide yields (up to?>95%) and enantioselectivities (up to 94% ee) have been achieved. The introduction of electron-withdrawing substituents leads to less active and less enantioselective catalysts. Like for the previously reported Ti-salalen catalyzed sulfoxidations, the temperature dependence of the sulfoxidation enantioselectivity in the presence of Ti-salan complexes is nonmonotonic, demonstrating isoinversion behavior with decreasing temperature. The oxidation is likely rate-limited by the formation of the active (presumably peroxotitanium(IV)) species, followed by a faster oxygen transfer to the substrate.
Asymmetric synthesis of esomeprazole
Cotton, Hanna,Elebring, Thomas,Larsson, Magnus,Li, Lanna,Soerensen, Henrik,Von Unge, Sverker
, p. 3819 - 3825 (2000)
A highly efficient synthesis of esomeprazole-the (S)-enantiomer of omeprazole-via asymmetric oxidation of prochiral sulphide 1 is described. The asymmetric oxidation was achieved by titanium-mediated oxidation with cumene hydroperoxide (CHP) in the presence of (S,S)-diethyl tartrate [(S,S)-DET]. The enantioselectivity was provided by preparing the titanium complex in the presence of 1 at an elevated temperature and/or during a prolonged preparation time and by performing the oxidation of 1 in the presence of an amine. An enantioselectivity of >94% ee was obtained using this method. Copyright (C) 2000 Elsevier Science Ltd.
Factors influencing the selectivity in asymmetric oxidation of sulfides attached to nitrogen containing heterocycles
Seenivasaperumal, Muthu,Federsel, Hans-Juergen,Ertan, Anne,Szabo, Kalman J.
, p. 2187 - 2189 (2007)
Asymmetric oxidation of heterocyclic sulfides, including imidazole, benzimidazole, indole and pyrimidine derivatives, were studied using a tartrate/Ti(iOPr)4 catalyst system. The Royal Society of Chemistry.
Asymmetric Bio-oxidation Using Resting Cells of Rhodococcus rhodochrous ATCC 4276 Mutant QZ-3 for Preparation of (S)-Omeprazole in a Chloroform–Water Biphasic System Using Response Surface Methodology
Zhang, Yuanyuan,Lv, Kuiying,Deng, Yashan,Li, Huiling,Wang, Zhiyong,Li, Depeng,Gao, Xin,Wang, Fanye
, p. 2928 - 2938 (2021)
(S)-Omeprazole is a very effective anti-ulcer medicine that is difficult to be prepared using whole cells at elevated substrate concentrations. In the chloroform–water biphasic system, resting cells of the mutant QZ-3 of Rhodococcus rhodochrous (R. rhodochrous) ATCC 4276 were used to catalyze the bio-oxidation of omeprazole sulfide for preparation of (S)-omeprazole. Using response surface methodology (RSM), the reaction was optimized to work at a substrate concentration of 180?mM and a cell concentration of 100?g/L. The optimal yield of (S)-omeprazole obtained was 92.9% with enantiomeric excess (ee) (> 99%), and no sulfone by-product was detected under the optimal working conditions; reaction temperature 37?°C, pH 7.3 and reaction time, 43?h. A quadratic polynomial model was established, which predicts the experimental data with very high accuracy (R2 = 0.9990). The chloroform–water biphasic system may contribute to the significant improvement in substrate tolerance because almost all substrates are partitioned in the organic phase (water solubility of omeprazole sulfide is only about 0.5?mg/mL), resulting in little damage and inhibition to cells by substrates. The mutant QZ-3 of R. rhodochrous ATCC 4276 exhibited high enantioselectivity, activity and substrate and product tolerance. The aerated flask provides enough oxygen for a high concentration of cells. Accordingly, bio-oxidation is thus more promising for efficient preparation of chiral sulfoxides.
Catalytic Asymmetric Synthesis of Esomeprazole by a Titanium Complex with a Hexa-aza-triphenolic Macrocycle Ligand
Song, Weiguo,Dong, Liangjun,Zhou, Yuhan,Fu, Yongqiang,Xu, Wenfang
, p. 70 - 77 (2015)
An efficient synthesis of esomeprazole via catalytic asymmetric oxidation of 1H-benzimidazolyl pyridinylmethyl sulfide by a titanium complex with a hexa-aza-triphenolic macrocycle ligand is described. Esomeprazole was prepared with 99.6% ee, which meets the high requirement of the European Pharmacopeia on enantiomeric purity.
Synthesis of optically active omeprazole by catalysis with vanadyl complexes with chiral Schiff bases
Koneva,Khomenko,Kurbakova,Komarova,Korchagina,Volcho,Salakhutdinov,Tolstikov,Tolstikov
, p. 1680 - 1685 (2008)
A new method for the preparation of optically active omeprazole, consisting in asymmetric oxidation of the corresponding sulfide with the use of vanadyl complexes with chiral Schiff bases as the catalysts has been elaborated. The best results of the oxidation were achieved by the use of the combination VO(acac)2-2-[{(1S,2S,3R,5S)-3-hydroxymethyl-2,6,6-trimethyl- bicyclo[3.1.1]hept-2-ylimino}methyl]phenol-N-ethyl-N,N-diisopropylamine.
Baeyer-Villiger Monooxygenase-Mediated Synthesis of Esomeprazole As an Alternative for Kagan Sulfoxidation
Bong, Yong Koy,Song, Shiwei,Nazor, Jovana,Vogel, Michael,Widegren, Magnus,Smith, Derek,Collier, Steven J.,Wilson, Rob,Palanivel,Narayanaswamy, Karthik,Mijts, Ben,Clay, Michael D.,Fong, Ryan,Colbeck, Jeff,Appaswami, Amritha,Muley, Sheela,Zhu, Jun,Zhang, Xiyun,Liang, Jack,Entwistle, David
, p. 7453 - 7458 (2018)
A wild-type Baeyer-Villiger monooxygenase was engineered to overcome numerous liabilities in order to mediate a commercial oxidation of pyrmetazole to esomeprazole, using air as the terminal oxidant in an almost exclusively aqueous reaction matrix. The developed enzyme and process compares favorably to the incumbent Kagan inspired chemocatalytic oxidation, as esomeprazole was isolated in 87% yield, in >99% purity, with an enantiomeric excess of >99%.
Asymmetric Sulfoxidation of Thioether Catalyzed by Soybean Pod Shell Peroxidase to Form Enantiopure Sulfoxide in Water-in-Oil Microemulsions: A Kinetic Model
Li, Huiling,Deng, Yashan,Du, ShanShan,Liu, Cui,Li, Kaiyuan,Xue, Xiao,Xu, Hui,Zhang, Yuanyuan,Yi, Tingting,Gao, Xin
, p. 2075 - 2086 (2021)
Esomeprazole with chiral sulfoxides structure is used to treat gastric ulcer disease. Soybean pod shell peroxidase (SPSP) is a peroxidase extracted from soybean pods shells which are one of the most abundant natural resources in the world. In the production of chiral sulfoxides catalyzed by SPSP, it is very important to establish the reaction kinetic model and explore the reaction mechanism for the development of the process, however, there is no report on the establishment of the model. Asymmetric sulfoxidation reactions catalyzed by SPSP in water-in-oil microemulsions were carried out, and the King-Altman approach was used to establish a kinetic model. A yield of 91% and e.e. value of 96% for esomeprazole were obtained at the activity of SPSP of 3200 U ml?1 and 50 °C for 5 h. The mechanism with a two-electron reduction of SPSP-I is accompanied with a single-electron transfer to SPSP-I and nonenzymatic reactions, indicating that three concomitant sub-mechanisms contribute to the asymmetric oxidation involving five enzymatic and two nonenzymatic reactions, which can represent the asymmetric sulfoxidation of organic sulfides to form enantiopure sulfoxides. With 5.44% of the average relative deviation, a kinetic model fitting experimental data was developed. The enzymatic reactions may follow ping-pong mechanism with substrate inhibition of H2O2 and product inhibition of esomeprazole, while nonenzymatic reactions follow a power law. Those results indicate that SPSP with a lower cost and higher thermal stability may be used as an effective substitute for horseradish peroxidase.
Resolution of omeprazole by inclusion complexation with a chiral host BINOL
Deng, Jingen,Chi, Yongxiang,Fu, Fangmin,Cui, Xin,Yu, Kaibai,Zhu, Jin,Jiang, Yaozhong
, p. 1729 - 1732 (2000)
Both (S)-(-)- and (R)-(+)-enantiomers of omeprazole were directly resolved by inclusion complexation with a chiral host compound (S)-(-)- or (R)-(+)-2,2'-dihydroxy-1,1'-binaphthyl in high enantiomeric excess (>99% e.e.). (C) 2000 Elsevier Science Ltd.
