4850-71-9Relevant academic research and scientific papers
Biocatalytic oxidation by chloroperoxidase from Caldariomyces fumago in polymersome nanoreactors
De Hoog,Nallani,Cornelissen,Rowan,Nolte,Arends
, p. 4604 - 4610 (2009)
The encapsulation of chloroperoxidase from Caldariomyces fumago (CPO) in block copolymer polymersomes is reported. Fluorescence and electron microscopy show that when the encapsulating conditions favour self-assembly of the block copolymer, the enzyme is incorporated with concentrations that are 50 times higher than the enzyme concentration before encapsulation. The oxidation of two substrates by the encapsulated enzyme was studied: i) pyrogallol, a common substrate used to assay CPO enzymatic activity and ii) thioanisole, of which the product, (R)-methyl phenyl sulfoxide, is an important pharmaceutical intermediate. The CPO-loaded polymersomes showed distinct reactivity towards these substrates. While the oxidation of pyrogallol was limited by diffusion of the substrate into the polymersome, the rate-limiting step for the oxidation of thioansiole was the turnover by the enzyme.
Preparation and Characterization of Optically Active Quadridentate Schiff Base-Titanium(IV) Complexes and the Catalytic Properties of These Complexes on Asymmetric Oxidation of Methyl Phenyl Sulfide with Organic Hydroperoxides
Sasaki, Caori,Nakajima, Kiyohiko,Kojima, Masaaki,Fujita, Junnosuke
, p. 1318 - 1324 (1991)
Titanium(IV) complexes, 2O, with quadridentate Schiff base ligands derived from optically active 1,2-diamines and salicylaldehyde were prepared by treating TiCl4 with an equimolar amount of the Schiff base ligand in wet pyridine.The com
Enantioselective Sulfoxidation of Thioanisole by Cascading a Choline Oxidase and a Peroxygenase in the Presence of Natural Deep Eutectic Solvents
Li, Yongru,Ma, Yunjian,Li, Peilin,Zhang, Xizhen,Ribitsch, Doris,Alcalde, Miguel,Hollmann, Frank,Wang, Yonghua
, p. 254 - 257 (2020)
A bienzymatic cascade for selective sulfoxidation is presented. The evolved recombinant peroxygenase from Agrocybe aegeritra catalyses the enantioselective sulfoxidation of thioanisole whereas the choline oxidase from Arthrobacter nicotianae provides the
Visible light-driven and chloroperoxidase-catalyzed oxygenation reactions
Perez, Daniel I.,Grau, Maria Mifsud,Arends, Isabel W. C. E.,Hollmann, Frank
, p. 6848 - 6850 (2009)
Robust peroxidase-catalyzed enantiospecific oxyfunctionalizations can be achieved by simple light-driven in situ generation of hydrogen peroxide.
Application of various ionic liquids as cosolvents for chloroperoxidase- catalysed biotransformations
Lichtenecker, Roman J.,Schmid, Walther
, p. 509 - 512 (2009)
Chloroperoxidase from Caldariomyces fumago catalyses oxidation of indole and thioanisole in reaction mixtures containing up to 40% (v/v) of different ionic liquids (ILs). Results indicate that ILs containing tosylate, trifluoroacetate, chloride, and methylsulfate anions are suitable cosolvents for these transformations, yielding high enantiomeric excess and good conversion rates.
Chiral separation materials based on derivatives of 6-amino-6-deoxyamylose
Gao, Ya-Ya,Zhang, Yu-Hang,Zhang, Shan,Chen, Wei,Bai, Zheng-Wu
supporting information, p. 899 - 914 (2021/10/07)
In order to develop new type of chiral separation materials, in this study, 6-amino-6-deoxyamylose was used as chiral starting material with which 10 derivatives were synthesized. The amino group in 6-amino-6-deoxyamylose was selectively acylated and then the hydroxyl groups were carbamoylated yielding amylose 6-amido-6-deoxy-2,3-bis(phenylcarbamate)s, which were employed as chiral selectors (CSs) for chiral stationary phases of high-performance liquid chromatography. The resulted 6-amido-6-deoxyamyloses and amylose 6-amido-6-deoxy-2,3-bis(phenylcarbamate)s were characterized by IR, 1H NMR, and elemental analysis. Enantioseparation evaluations indicated that most of the CSs demonstrated a moderate chiral recognition capability. The 6-nonphenyl (6-nonPh) CS of amylose 6-cyclohexylformamido-6-deoxy-2,3-bis(3,5-dimethylphenylcarbamate) showed the highest enantioselectivity towards the tested chiral analytes; the phenyl-heterogeneous (Ph-hetero) CS of amylose 6-(4-methylbenzamido)-6-deoxy-2,3-bis(3,5-dimethylphenylcarbamate) baseline separated the most chiral analytes; the phenyl-homogeneous (Ph-homo) CS of amylose 6-(3,5-dimethylbenzamido)-6-deoxy-2,3-bis(3,5-dimethylphenylcarbamate) also exhibited a good enantioseparation capability among the developed CSs. Regarding Ph-hetero CSs, the enantioselectivity depended on the combination of the substituent at 6-position and that at 2- and 3-positions; as for Ph-homo CSs, the enantioselectivity was related to the substituent at 2-, 3-, and 6-positions; with respect to 6-nonPh CSs, the retention factor of most analytes on the corresponding CSPs was lower than that on Ph-hetero and Ph-homo CSPs in the same mobile phases, indicating π–π interactions did occur during enantioseparation. Although the substituent at 6-position could not provide π–π interactions, the 6-nonPh CSs demonstrated an equivalent or even higher enantioselectivity compared with the Ph-homo and Ph-hetero CSs.
Ionic liquid-functionalized amphiphilic Janus nanosheets afford highly accessible interface for asymmetric catalysis in water
Li, Chaoping,Liu, Su,Pi, Yibing,Feng, Jingwen,Liu, Zewei,Li, Shiye,Tan, Rong
, p. 236 - 245 (2021/02/16)
High oil/water interfacial area together with accessible interfaces for regents is the key to achieving efficient asymmetric catalysis in water. Herein, by taking advantage of the excellent interfacial activity of Janus nanosheets (JNS), as well as the unique compatibility of imidazolium ionic liquid (IL), we developed a series of IL-functionalized amphiphilic Janus mesosilica nanosheets which afford highly accessible reaction interfaces for highly enantioselective sulfoxidation in water. The JNS-typed chiral salen TiIV catalysts were prepared by selectively decorating hydrophobic chiral salen TiIV complex on one side of Janus mesosilica nanosheets through the imidazolium-based IL linker. Benefiting from the two-dimensional porous Janus structure, as well as the compatible IL linker, the IL-tagged JNS catalysts afforded high oil/water interfacial areas and highly accessible reaction interface for sulfides and H2O2, significantly accelerating asymmetric sulfoxidation in water using H2O2 as an oxidant. In addition, they can be facilely recovered for stable reuse by simple centrifugation.
Two enantiocomplementary Baeyer-Villiger monooxygenases newly identified for asymmetric oxyfunctionalization of thioether
Liu, Yafei,Ni, Ye,Wei, Shiyu,Xu, Guochao,Zhou, Jieyu
, (2021/08/19)
Two enantiocomplementary Baeyer-Villiger monooxygenases RaBVMO and AmBVMO were identified by genome mining for the asymmetric sulfoxidation. Both recombinant BVMOs have optimal pH of 9.0 and temperature of 35 °C. The half-lives of RaBVMO and AmBVMO at 30 °C were 24.4 and 24.6 h. RaBVMO and AmBVMO exhibited broad substrate spectrum and could catalyze the oxidization of various compounds including fatty ketones, cyclic ketones, and thioethers. Kinetic parameters analysis revealed that both RaBVMO and AmBVMO displayed higher catalytic efficiency toward thioanisole than cyclohexanone. As much as 50 mM thioanisole could be completely oxidized by AmBVMO and RaBVMO with 99% (R) and 95% (S), respectively. Molecular docking analysis further provides evidence for the complementary enantioselectivity of RaBVMO and AmBVMO. Our results demonstrate the potential application of the two novel BVMOs in asymmetric synthesis of sulfoxides.
Efficient Synthesis of Sulfur-Stereogenic Sulfoximines via Ru(II)-Catalyzed Enantioselective C-H Functionalization Enabled by Chiral Carboxylic Acid
Zhou, Tao,Qian, Pu-Fan,Li, Jun-Yi,Zhou, Yi-Bo,Li, Hao-Chen,Chen, Hao-Yu,Shi, Bing-Feng
supporting information, p. 6810 - 6816 (2021/05/29)
Ru(II)-catalyzed enantioselective C-H functionalization involving an enantiodetermining C-H cleavage step remains undeveloped. Here we describe a Ru(II)-catalyzed enantioselective C-H activation/annulation of sulfoximines with α-carbonyl sulfoxonium ylides using a novel class of chiral binaphthyl monocarboxylic acids as chiral ligands, which can be easily and modularly prepared from 1,1′-binaphthyl-2,2′-dicarboxylic acid. A broad range of sulfur-stereogenic sulfoximines were prepared in high yields with excellent enantioselectivities (up to 99% yield and 99% ee) via desymmetrization, kinetic resolution, and parallel kinetic resolution. Furthermore, the resolution products can be easily transformed to chiral sulfoxides and key intermediates for kinase inhibitors.
The mutagenesis of a single site for enhancing or reversing the enantio- or regiopreference of cyclohexanone monooxygenases
Hu, Yujing,Xu, Weihua,Hui, Chenggong,Xu, Jian,Huang, Meilan,Lin, Xianfu,Wu, Qi
supporting information, p. 9356 - 9359 (2020/11/02)
The mutagenesis of a "second sphere"switch residue of CHMOAcineto could control its enantio- and regiopreference. Replacing phenylalanine (F) at position 277 of CHMOAcineto into larger tryptophan (W) enabled a significant enhancement of enantio- or regioselectivity toward structurally diverse substrates, moreover, a complete reversal of enantio- or regiopreference was realized by mutating F277 into a range of smaller amino acids (A/C/D/E/G/H/I/K/L/M/N/P/Q/R/S/T/V).
