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Relevant academic research and scientific papers

Accessing Enantiopure Epoxides and Sulfoxides: Related Flavin-Dependent Monooxygenases Provide Reversed Enantioselectivity

Enantiopure organic compounds are of major importance for the chemical and pharmaceutical industry. Flavin-dependent group E monooxygenases, composed of monooxygenase and reductase, are known to perform epoxidation of substituted alkenes as well as sulfoxidation in a regio- and enantioselective fashion. Group E is divided into styrene monooxygenases (SMO) and indole monooxygenases (IMO). Hitherto mainly SMOs have been characterized. In this study, we assayed 31 monooxygenases from both types, while 23 of which showed activity. They almost exclusively produced (S)-styrene oxide at high enantiomeric excess with maximum activities of 0.73 μmol min?1 mg?1 (kcat=0.54 s?1). In case of sulfoxidation, we found that the enantioselectivity is contrary between both types. IMOs preferably produce the (S)-enantiomer while SMOs have a tendency to produce the (R)-enantiomer. Sequence analysis and molecular docking of substrates allowed identifying fingerprint motives: SMO N46-V48-H50-Y73-H76-S96 and IMO S46-Q48-M50-V/I73-I76-A96. These form an essential part of the active site while the loop (AS44-51) interacts with the co-substrate and other amino acids direct the substrate. The motives clearly distinguish group E monooxygenases and define the enantioselectivity and thus direct biotechnological applications. Two-hour biotransformations with several sulfides in conjunction with upscale experiments (10 and 100 mg scale) resulted in the identification of promising candidates for the realization of biocatalytic processes.

Highly Efficient Access to (S)-Sulfoxides Utilizing a Promiscuous Flavoprotein Monooxygenase in a Whole-Cell Biocatalyst Format

Chiral sulfoxides have gained attention as synthons and precursors for API synthesis. Flavoproteins such as Baeyer-Villiger or styrene monooxygenases mainly provide access to (R)-sulfoxides and often suffer from low selectivity, activity, and/or limited substrate scope. The flavoprotein monooxygenase AbIMO from Acinetobacter baylyi ADP1 initiates indole degradation. Here, AbIMO was expressed recombinantly in E. coli and characterized for its sulfoxidation activity and substrate spectrum. Next to indole and styrene, AbIMO was found to accept numerous alkyl aryl sulfides as substrates, transforming them to (S)-sulfoxides with high enantioselectivity (95 percent to '99 percent for most sulfides). The formulation as a whole-cell biocatalyst allowed specific production rates of up to 370 U gcdw?1 – the highest specific oxygenase activity achieved in whole cells so far – and the preparative synthesis of enantiopure (S)-aryl alkyl sulfoxides. With its extraordinarily high specific activity, high specificity, ease of handling, and high stability (catalyst is stable for '16 days at 4 °C), the designed whole-cell biocatalyst adds enormous value to the portfolio of chemical and biological catalysts for asymmetric sulfoxide synthesis.

A novel homochiral metal-organic framework with an expanded open cage based on (: R)-3,3′-bis(6-carboxy-2-naphthyl)-2,2′-dihydroxy-1,1′-binaphthyl: synthesis, X-ray structure and efficient HPLC enantiomer separation

A new homochiral metal-organic framework (MOF) with an expanded open cage based on the (R)-3,3′-bis(6-carboxy-2-naphthyl)-2,2′-dihydroxy-1,1′-binaphthyl ligand was synthesized and utilized as a novel chiral stationary phase for high-performance liquid chromatography. Twelve racemates including sec-alcohols, sulfoxides, epoxides, lactone, 1,3-dioxolan-2-one, and oxazolidinone were used as analytes for evaluating the separation properties of the chiral-MOF-packed column. Experimentally, the homochiral MOF offered good molecular recognition ability, which suggests good prospects for the application of chiral MOFs as stationary phases for enantioseparation.

Peroxygenase-Catalyzed Enantioselective Sulfoxidations

The performances of the unspecific peroxigenase from Agrocybe aegerita (AaeUPO) in the asymmetric sulfoxidation of substituted aryl alkyl sulfides were here investigated. A small library of differently substituted aryl alkyl sulfoxides was successfully synthesized from the corresponding sulfides in the presence of AaeUPO and H2O2. All the sulfoxides were obtained as (R)-enantiomers, regardless the substitution pattern both on the aromatic ring and the alkyl chain, in up to > 99 % conversion and > 99 % ee. An overview about the biocatalytic entries to chiral sulfoxides is also presented here in form of a comparison between the results obtained with AaeUPO and performances of the chloroperoxidase from Caldariomyces fumago, and three different Baeyer–Villiger monooxygenases. To the best our knowledge, this is the first example of a systematic investigation of the AaeUPO synthetic potential in the asymmetric oxidation of hetero atoms, i.e., the pro-stereogenic sulfur of sulfides.

Stereoselective sulfoxidation catalyzed by achiral Schiff base complexes in the presence of serum albumin in aqueous media

Four coordination complexes ML derived from an achiral Schiff base ligand (H2L = 2,2′-[(1,2-ethanediyl)bis(nitrilopropylidyne)]bisphenol) have been synthesized and characterized. A method is described for the enantioselective oxidation of a series of aryl alkyl sulfides using the coordination complexes in the presence of serum albumins (SAs) in an aqueous medium at ambient temperature. The mixture of metal complexes with serum albumins is useful for inducing asymmetric catalysis. The complex, albumin source and substrate influence stereoselective sulfoxidation. At optimal pH with the appropriate oxidant, some of ML/SA systems are identified as very efficient catalysts, giving the corresponding sulfoxides in excellent chemical yield (up to 100%) and good enantioselectivity (up to 94% ee) in certain cases. UV–visible spectroscopic data provide evidence that stronger binding between the complex and serum albumin lead to higher enantioselectivity.

Enantioselective Aromatic Sulfide Oxidation and Tandem Kinetic Resolution Using Aqueous H2O2 and Chiral Iron–Bis(oxazolinyl)bipyridine Catalysts

An efficient method for the oxidation of aromatic sulfides has been developed by using aqueous H2O2, catalyzed by the in situ generated chiral Fe/6,6′-bis(4-isopropyloxazolin-2-yl)-2,2′-bipyridine (bipybox-iPr) complex. The corresponding sulfoxides were obtained with high enantioselectivities (up to 98.5:1.5 er) and in good yields (up to 61 %) when the mono-oxidation of the sulfides was performed in combination with the kinetic resolution of the sulfoxide into the sulfone.

HPLC enantioseparation on a homochiral MOF-silica composite as a novel chiral stationary phase

The last frontier in the development of chiral stationary phases for chromatographic enantioseparation involves homochiral metal-organic frameworks (MOFs). Using enantiopure (R)-2,2′-dihydroxy-1,1′-binaphthalene-6,6′-dicarboxylic acid as a starting material, we prepared three homochiral MOFs that were further used as chiral stationary phases for high-performance liquid chromatography to separate the enantiomers of various kinds of racemic sulfoxides, sec-alcohols, β-lactams, benzoins, flavanones and epoxides. The experimental results showed excellent performances for enantioseparation, and highlighted that enantioseparation on homochiral MOF columns is practical.

Efficient HPLC enantiomer separation using a pillared homochiral metal-organic framework as a novel chiral stationary phase

HPLC enantioseparation of racemates using novel pillared homochiral metal-organic framework-silica composite as chiral stationary phase has been successfully demonstrated.

Asymmetric catalytic sulfoxidation by a novel v IV 8 cluster catalyst in the presence of serum albumin: A simple and green oxidation system

A novel VIV8 cluster formulated as [V8O12(OH)4(CH3O)4(DAC)4]·7CH3OH (1) (DAC = 1,2-diaminocyclohexane) has been constructed successfully. Enantioselective oxidation of a series of alkyl aryl sulfides catalyzed by 1 is tested in an aqueous medium in the presence of serum albumin. The catalytic procedure is found to be simple and environmentally friendly. The influences of the parameters such as concentration of catalyst and oxidant, pH, and reaction time on the thioanisole as models are investigated. Under optimum conditions, 1 exhibits high conversion (up to 99%), excellent chemoselectivity (≥90% in all cases) and moderate enantioselectivity (up to 75% ee). After binding with serum albumin, the catalytic activity of 1 is promoted. The bovine serum albumin (BSA) and pig serum albumin (PSA) molecules have a more positive effect on the catalytic activity.

Bovine serum albumin-cobalt(II) Schiff base complex hybrid: An efficient artificial metalloenzyme for enantioselective sulfoxidation using hydrogen peroxide

An artificial metalloenzyme (BSA-CoL) based on the incorporation of a cobalt(ii) Schiff base complex {CoL, H2L = 2,2′-[(1,2-ethanediyl)bis(nitrilopropylidyne)]bisphenol} with bovine serum albumin (BSA) has been synthesized and characterized. Attention is focused on the catalytic activity of this artificial metalloenzyme for enantioselective oxidation of a variety of sulfides with H2O2. The influences of parameters such as pH, temperature, and the concentration of catalyst and oxidant on thioanisole as a model are investigated. Under optimum conditions, BSA-CoL as a hybrid biocatalyst is efficient for the enantioselective oxidation of a series of sulfides, producing the corresponding sulfoxides with excellent conversion (up to 100%), chemoselectivity (up to 100%) and good enantiomeric purity (up to 87% ee) in certain cases.