A new titanate/(+)-(1R,2S)-cis-1-amino-2-indanol system for the asymmetric synthesis of (S)-tenatoprazole

Delamare, Madeleine; Belot, Sébastien; Caille, Jean-Claude; Martinet, F.; Kagan, Henri B.; Henryon, Vivien

doi:10.1016/j.tetlet.2009.01.111

Cited by 18 publications

(7 citation statements)

References 12 publications

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“…Optically active sulfoxides are important chiral intermediates for asymmetric synthesis, and these sulfoxides also constitute the structure of pharmaceuticals, such as prazoles, which are proton pump inhibitors (PPIs) (12)(13)(14). Although metal catalysts, such as titanate/(ϩ)-(1R,2S)-cis-1-amino-2-indanol and vanadium/chitosan systems, have been used in the asymmetric oxidation of prazole thioethers (13,(15)(16)(17)(18)(19)(20), the practical utilization of heavy metals, expensive chiral ligands, and compounds with relatively low stereo-and chemoselectivity is hampered because they are environmentally detrimental. In contrast, biooxidation approaches have rapidly been developed in recent years (Fig.…”

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confidence: 99%

Discovery of Two Native Baeyer-Villiger Monooxygenases for Asymmetric Synthesis of Bulky Chiral Sulfoxides

Zhang

Liu

et al. 2018

Appl Environ Microbiol

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Two Baeyer-Villiger monooxygenases (BVMOs), designated BVMO andBVMO, were discovered from and, respectively. Both monooxygenases displayed novel features for catalyzing the asymmetric sulfoxidation of bulky and pharmaceutically relevant thioethers. Evolutionary relationship and sequence analysis revealed that the two BVMOs belong to the family of typical type I BVMOs and the subtype ethionamide monooxygenase. Both BVMOs are active toward medium- and long-chain aliphatic ketones as well as various thioether substrates but are ineffective toward cyclohexanone, aromatic ketones, and other typical BVMO substrates. BVMO andBVMO showed the highest activities (0.117 and 0.025 U/mg protein, respectively) toward thioanisole among the tested substrates. Furthermore, these BVMOs exhibited distinct activity and excellent stereoselectivity toward bulky and prochiral prazole thioethers, which is a unique feature of this family of BVMOs. No native enzyme has been reported for the asymmetric sulfoxidation of bulky prazole thioethers into chiral sulfoxides. The identification of BVMO andBVMO provides an important scaffold for discovering enzymes capable of asymmetrically oxidizing bulky thioether substrates by genome mining. Baeyer-Villiger monooxygenases (BVMOs) are valuable enzyme catalysts that are an alternative to the chemical Baeyer-Villiger oxidation reaction. Although BVMOs display broad substrate ranges, no native enzymes were reported to have activity toward the asymmetric oxidation of bulky prazole-like thioether substrates. Herein, we report the discovery of two type I BVMOs from (BVMO) and (BVMO) which are able to catalyze the asymmetric sulfoxidation of bulky prazole thioethers (proton pump inhibitors [PPIs], a group of drugs whose main action is a pronounced and long-lasting reduction of gastric acid production). Efficient catalysis of omeprazole oxidation by BVMO was developed, indicating that this enzyme is a promising biocatalyst for the synthesis of bulky and pharmaceutically relevant chiral sulfoxide drugs. These results demonstrate that the newly identified enzymes are suitable templates for the discovery of more and better thioether-converting BVMOs.

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confidence: 99%

Discovery of Two Native Baeyer-Villiger Monooxygenases for Asymmetric Synthesis of Bulky Chiral Sulfoxides

Zhang

Liu

et al. 2018

Appl Environ Microbiol

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“…Only the N -methyl-substituted derivative led to a ( S ) product with a moderate ee (up to 56%). Another aminoalcohol, (1 R ,2 S )- cis -1-amino-2-indanol ( 200 ), led to the optimal results (90% yield, 99% ee ) in the synthesis of ( S )-tenatoprazole 201 . The reaction was carried out in 1-methyl-2-pyrrolidine as a solvent at 0 °C in the presence of 0.5 equiv of Ti(O -i Pr) 4 and 2.32 equiv of CHP.…”

Section: Chemical Methods Of Nonracemic Sulfoxide Preparationmentioning

confidence: 99%

Enantioselective Synthesis of Sulfoxides: 2000−2009

2010

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Elz ˙bieta Wojaczyn ´ska (ne ´e Ostrycharz) was born in Z ˙migród, Poland. She received her M.Sc. degree in organic chemistry from Wrocław University of Technology in 1997. Her doctoral thesis on the enantioselective synthesis and application of chiral sulfoxides was completed under the supervision of Professor Jacek Skarz ˙ewski in 2001. Her research at the Department of Organic Chemistry of the Wrocław University of Technology focuses on the synthesis of new chiral building blocks and of novel chiral ligands for the asymmetric synthesis. Jacek Wojaczyn ´ski was born in Wrocław in 1969. He graduated from the University of Wrocław in inorganic chemistry in 1993. He received his Ph.D. in 1998 for work on the influence of asymmetric modification of the porphyrin periphery on the properties of formed complexes. He is a member of the Porphyrin Chemistry Research Group led by Professor Lechosław Latos-Graz ˙yn ´ski at the Department of Chemistry, University of Wrocław. His current scientific interests include degradation of tetrapyrrolic macrocycles and investigation of paramagnetic hemoproteins using NMR spectroscopy.

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“…8 The deprotected chiral reaction product, ĲR)-2-hydroxy-1-indanone, then serves as a vicinal hydroxy ketone building block for further utilization, e.g., for production of cis-1-amino-2-indanol, a widely utilized intermediate for pharmaceuticals, chiral catalysts, chiral auxiliaries and chiral resolving agents. [17][18][19][20][21][22][23][24] The main methodologies traditionally utilized for the preparation of chiral compounds are based on classical racemate resolution, asymmetric synthesis, and kinetic resolution. Enzymatic kinetic resolution of racemic starting materials is a useful tool for obtaining enantiomerically pure products, being, however, limited to the maximum theoretical yield of 50%.…”

Section: Introductionmentioning

confidence: 99%

One-pot synthesis of (R)-2-acetoxy-1-indanone from 1,2-indanedione combining metal catalyzed hydrogenation and chemoenzymatic dynamic kinetic resolution

Långvik

Sandberg

Wärnå

et al. 2015

Catal. Sci. Technol.

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A new titanate/(+)-(1R,2S)-cis-1-amino-2-indanol system for the asymmetric synthesis of (S)-tenatoprazole

Cited by 18 publications

References 12 publications

Discovery of Two Native Baeyer-Villiger Monooxygenases for Asymmetric Synthesis of Bulky Chiral Sulfoxides

Discovery of Two Native Baeyer-Villiger Monooxygenases for Asymmetric Synthesis of Bulky Chiral Sulfoxides

Enantioselective Synthesis of Sulfoxides: 2000−2009

One-pot synthesis of (R)-2-acetoxy-1-indanone from 1,2-indanedione combining metal catalyzed hydrogenation and chemoenzymatic dynamic kinetic resolution

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