326602-80-6Relevant academic research and scientific papers
Structure-induced catalysis enhancement of Cu-amino catalysts for rapidly selective oxidation of sulfides in the presence of H2O2
Zhang, Zhi-Hui,Yang, Xu-Sheng,Zhang, Qing-Qing,Wang, Liang,He, Ming-Yang,Chen, Qun,Huang, Xian-Feng
, p. 104036 - 104040 (2016)
With benzyl phenyl sulfide as a model substrate and H2O2 as an oxidant, high selectivity toward the desired sulfoxide is obtained when using two CuII-amino acid complexes as catalysts, while strong stereospecific obstruction in a 1D helical array of complex 2 enables speedy sulfoxidation with excellent conversion.
Synthetic method and application of omeprazole
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Paragraph 0045; 0048-0049; 0051-0054, (2021/07/17)
The invention belongs to the field of medicine synthesis, and discloses a synthetic method of omeprazole. The synthetic method comprises the following steps: reacting sodium (4-methoxy-3, 5-dimethyl pyridine-2-yl) methanesulfinate to generate (4-methoxy-3, 5-dimethyl pyridine-2-yl) methanesulfinic acid acyl chloride, and then carrying out Suzuki reaction on the (4-methoxy-3, 5-dimethyl pyridine-2-yl) methanesulfinic acid acyl chloride and (6-methoxy-1H-benzo [d] imidazole-2-yl) boric acid to generate omeprazole. According to the synthetic method of omeprazole, the omeprazole which is easy to purify and stable in yield is obtained by using raw materials which are easy to obtain, and a synthetic method which is simple, easy to operate and control, mild in reaction condition and capable of replacing high-risk reagents such as butyl lithium and the like by using a common reagent. The invention also provides an application of the synthetic method of omeprazole. The synthetic method is suitable for synthesis of omeprazole. The obtained omeprazole is used for preparing an omeprazole injection.
Integrating hydrogen production with anodic selective oxidation of sulfides over a CoFe layered double hydroxide electrode
Ma, Lina,Zhou, Hua,Xu, Ming,Hao, Peipei,Kong, Xianggui,Duan, Haohong
, p. 938 - 945 (2021/02/06)
Replacing the sluggish oxygen evolution reaction (OER) with oxidation reactions for the synthesis of complex pharmaceutical molecules coupled with enhanced hydrogen evolution reaction (HER) is highly attractive, but it is rarely explored. Here, we report an electrochemical protocol for selective oxidation of sulfides to sulfoxides over a CoFe layered double hydroxide (CoFe-LDH) anode in an aqueous-MeCN electrolyte, coupled with 2-fold promoted cathodic H2productivity. This protocol displays high activity (85-96% yields), catalyst stability (10 cycles), and generality (12 examples) in selective sulfide oxidation. We demonstrate its applicability in the synthesis of four important pharmaceutical related sulfoxide compounds with scalability (up to 1.79 g). X-ray spectroscopy investigations reveal that the CoFe-LDH material evolved into amorphous CoFe-oxyhydroxide under catalytic conditions. This work may pave the way towards sustainable organic synthesis of valuable pharmaceuticals coupled with H2production.
Synthesis method of esomeprazole serving as proton pump inhibitor
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Paragraph 0032; 0035; 0036; 0039; 0040; 0043; 0044; 0047, (2019/11/20)
The invention discloses a synthesis method of esomeprazole serving as a proton pump inhibitor, and belongs to the technical field of drug synthesis. According to the method, asymmetric oxidation on isconducted on omeprazole thioether under the condition that chiral phosphoric acid serves as a catalyst and hydrogen peroxide serves as an oxidizing agent to generate esomeprazole. Firstly, 5-methoxy-2-benzimidazolethiol and 2-chloromethyl-4-methoxy-3,5-dimethylpyridine hydrochloride generate omeprazole thioether in an aqueous phase, and then selective oxidation is conducted on omeprazole in the presence of a chiral phosphoric acid catalyst to generate esomeprazole. The method has the advantages of being high in yield, environmentally friendly, good in selectivity, free of heavy metal residuesand more suitable for large-scale industrial production.
Tartaric acid ester compound as well as preparation method and applications thereof
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Paragraph 0101-0106, (2019/03/29)
The invention discloses a compound shown in formula (I), wherein R1 and R2 are independently selected from optionally substituted C1-6 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted C6-14 aryl and optionally substituted -(CH2)m-C3-8 cycloalkyl or -(CH2)n Ar; and Ar denotes the optionally substituted C6-14 aryl. The compound can be used for preparing prazole drugs during thetitanium-catalyzed asymmetric oxidation of pyrazole sulfides. (img file='DDA0001401304200000011.TIF' wi='669' he='551'/).
Selective Late-Stage Oxygenation of Sulfides with Ground-State Oxygen by Uranyl Photocatalysis
Li, Yiming,Rizvi, S. Aal-e-Ali,Hu, Deqing,Sun, Danwen,Gao, Anhui,Zhou, Yubo,Li, Jia,Jiang, Xuefeng
supporting information, p. 13499 - 13506 (2019/08/21)
Oxygenation is a fundamental transformation in synthesis. Herein, we describe the selective late-stage oxygenation of sulfur-containing complex molecules with ground-state oxygen under ambient conditions. The high oxidation potential of the active uranyl cation (UO22+) enabled the efficient synthesis of sulfones. The ligand-to-metal charge transfer process (LMCT) from O 2p to U 5f within the O=U=O group, which generates a UV center and an oxygen radical, is assumed to be affected by the solvent and additives, and can be tuned to promote selective sulfoxidation. This tunable strategy enabled the batch synthesis of 32 pharmaceuticals and analogues by late-stage oxygenation in an atom- and step-efficient manner.
Sulfoxide and sulfone compounds, as well as selective synthesis method and application thereof
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Paragraph 0045-0048; 0190-0193, (2019/12/02)
The invention discloses a method for selectively synthesizing a sulfoxide compound shown as a formula (II) and a sulfone compound shown as a formula (III). In a reaction solvent, thioether (I) is usedas a reaction raw material and oxygen as an oxidation reagent, under the catalytic action of visible light and a photosensitive reagent; under the assistance of an additive, when a large-polarity proton-containing additive such as an acid and an alcohol or a solvent or an additive with excellent electron donating ability is used, a sulfoxide compound (II) is selectively generated; and when a small-polarity aprotic additive or a solvent is used, a sulfone compound (III) is selectively generated. The synthesis method has the advantages of easily available and cheap raw materials, simple reaction operation, mild reaction conditions, high yield and excellent functional group tolerance. According to the invention, synthesis and modification of some medicines are realized, and an efficient method for selectively constructing sulfoxide and sulfone compounds is provided for medicinal chemistry research.
A catalytic asymmetric oxidizing thioether preparation of chiral pharmaceutical method
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Paragraph 0038-0044, (2020/02/07)
The invention provides a preparation method of a chiral sulfoxide medicament though catalysis of asymmetric oxidation of sulfides compounds. A chiral complex formed by quadridentate nitrogen organic ligand and metal manganese compound as a catalyst and hydrogen peroxide as an oxidant are used for asymmetric catalytic oxidation of prochiral thioether compound, so as to obtain the corresponding chiral sulfoxide medicament compounds including S-omeprazole, S-lansoprazole, S-pantoprazole, S-rabeprazole, R-Modafinil and R-sulindac. The reaction has the advantages of cleaness, mild reaction conditions, high conversion rate and antipodal selectivity, and shows industrial prospects.
Oxidative kinetic resolution of heterocyclic sulfoxides with a porphyrin-inspired manganese complex by hydrogen peroxide
Yang, Jinchuang,Wang, Lianyue,Lv, Ying,Li, Ning,An, Yue,Gao, Shuang
supporting information, p. 156 - 159 (2017/12/15)
We have successfully reported here the low loading porphyrin-inspired high-valent manganese (IV)-oxo complex was applied in oxidative kinetic resolution (OKR) of racemic heterocyclic sulfoxides using the environmentally benign hydrogen peroxide for the first time. This approach allows for rapid OKR (0.5 h) of a variety of racemic sulfoxides (including pyridine, pyrimidine, pyrazine, thiazole, benzothiazole, thiophene) in excellent enantioselectivity (up to > 99% ee), simultaneously generating the corresponding sulfones in high yield (up to 80%). The catalytic system also showed an unexceptionable chemoselectivity for the sulfoxide substrates with hydroxyl groups in which only the sulfoxide group was oxidized. The practical utility of the method has been demonstrated in the OKR of gram-scale sulfoxides.
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 (2018/10/09)
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.
