Stereoselective formation of aromatic sulphoxides by oxidation of sulphides and sulphoxides in the presence of bovine serum albumin

Sugimoto, Toyonari; Kokubo, Toshio; Miyazaki, Jinsei; Tanimoto, Shigeo; Okano, Masaya

doi:10.1039/c39790001052

Cited by 18 publications

(4 citation statements)

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“…Catalytic enantioselective oxidation of sulfides by various oxidants in the presence of bovine serum albumin (BSA) was investigated by Sugimoto and Kokubo et al in the late 1970’s. − In one publication, the effect of stoichiometric metal additives, namely Cu(II), MoO 4 2– , or WO 4 2– , in combination with t -BuOOH was reported, though the results were less promising than other systems tested in terms of yield and selectivity . In 1983, T. Kokubo et al investigated the asymmetric OsO 4 -catalyzed dihydroxylation of alkenes with BSA as a scaffold with remarkable success (Scheme ).…”

Section: Historical Contributionsmentioning

confidence: 99%

Artificial Metalloenzymes: Reaction Scope and Optimization Strategies

et al. 2017

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The incorporation of a synthetic, catalytically competent metallocofactor into a protein scaffold to generate an artificial metalloenzyme (ArM) has been explored since the late 1970's. Progress in the ensuing years was limited by the tools available for both organometallic synthesis and protein engineering. Advances in both of these areas, combined with increased appreciation of the potential benefits of combining attractive features of both homogeneous catalysis and enzymatic catalysis, led to a resurgence of interest in ArMs starting in the early 2000's. Perhaps the most intriguing of potential ArM properties is their ability to endow homogeneous catalysts with a genetic memory. Indeed, incorporating a homogeneous catalyst into a genetically encoded scaffold offers the opportunity to improve ArM performance by directed evolution. This capability could, in turn, lead to improvements in ArM efficiency similar to those obtained for natural enzymes, providing systems suitable for practical applications and greater insight into the role of second coordination sphere interactions in organometallic catalysis. Since its renaissance in the early 2000's, different aspects of artificial metalloenzymes have been extensively reviewed and highlighted. Our intent is to provide a comprehensive overview of all work in the field up to December 2016, organized according to reaction class. Because of the wide range of non-natural reactions catalyzed by ArMs, this was done using a functional-group transformation classification. The review begins with a summary of the proteins and the anchoring strategies used to date for the creation of ArMs, followed by a historical perspective. Then follows a summary of the reactions catalyzed by ArMs and a concluding critical outlook. This analysis allows for comparison of similar reactions catalyzed by ArMs constructed using different metallocofactor anchoring strategies, cofactors, protein scaffolds, and mutagenesis strategies. These data will be used to construct a searchable Web site on ArMs that will be updated regularly by the authors.

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Section: Historical Contributionsmentioning

confidence: 99%

Artificial Metalloenzymes: Reaction Scope and Optimization Strategies

et al. 2017

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“…Oxidations and reductions were the rst and are the most studied transformations promoted by albumin. The pivotal reports by Sugimoto 6,7 have been followed by the oxidation of sulfur-containing compounds, [72][73][74] the epoxidation of electron-decient olens, 75 and the reduction of d-ketoacids to the corresponding enantio-enriched lactones, 76 to cite only a few. The literature of these reactions was covered by an exhaustive review that appeared in 2004.…”

Section: Sulde Oxidationmentioning

confidence: 99%

“…[1][2][3][4][5] In 1978 Sugimoto developed the rst enantioselective reduction of prochiral ketones in aqueous buffer promoted by BSA, 6 followed a year later by enantioselective sulfoxidation. 7 Aerwards, at least in some cases, the amount of protein could be reduced to catalytic levels, thus greatly increasing the simplicity of work-up and the efficiency of the protocol without affecting the stereoselectivity.…”

Section: Introductionmentioning

confidence: 99%

Albumin as a promiscuous biocatalyst in organic synthesis

Albanese

Gaggero

2015

RSC Adv.

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“…Actively grown or 'resting-cells' of fungi have been widely used to obtain sulphoxides in good optical yields (Auret et al, 1968;Abushanab et al, 1978;Holland et al, 1985). Other methods of biotransformation such as the use of enzymes of mammalian origin Takata et al, 1983) or peroxide oxidation in the presence of enzyme templates (Sugimoto et al, 1981) are, however, not generally applicable to preparative scale work.…”

Section: Introductionmentioning

confidence: 99%

Biocatalysts for production of chiral epoxides

Mahmoudian

Michael

1992

Appl Microbiol Biotechnol

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An extensive screen for microorganisms capable of growth on olefins was carried out. Over 100 bacterial strains (mesophilic, thermophilic) were isolated in pure culture with gaseous or liquid (internal & terminal) olefins as the sole source of carbon and energy. The organisms included Aero coccus, Aeromonas,Alcaligenes, Flavobacterium, Micrococcus, Moraxella, Nocardia, Pseudomonas, Staphylococcus, Streptomyces and Vibrio spp. and a variety of Gram-negative, Gram-positive and Gram-variable rods/coccobacilli not yet identified. Given the success of isolating many different genera of alkene-utilizing bacteria, it would suggest that the ability to utilize olefin hydrocarbons is more widespread in nature than previously recognized.Initial studies involved testing a collection of strains for i) growth rate on the substrate of isolation and ii) evidence of epoxide accumulation from lower gaseous olefins. All of the 18 ethene-and propene-utilizing bacteria tested, stereospecifically formed R-1,2-epoxypropane (ee=90-96%), R -l,2-epoxybutane (ee=90-98%) and trans-(2/?,37?)-epoxybutane (ee=64-88%), as analyzed by chiral complexation glc. A particularly promising strain of Micrococcus sp. M90C was selected to demonstrate: a) Induction of epoxidation activity in carbohydrate-grown cells. b) Optimization of a biotransformation process for production of epoxyethane. c) Involvement of a specific monooxygenase in the formation of chiral epoxides. d) Stereoselectivity of epoxyalkane degradation. e) Substrate specificity toward a range of olefins.Micrococcus sp. M90C stereospecifically formed S-(+)-phenyl glycidyl ether (ee=93%) and /?-(+)-phenyl methyl sulphoxide (ee>98%), as analyzed by chiral-shift NMR and HPLC. The ability to catalyze heteroatom oxygenation as well as epoxidation of a wide range of olefins in high optical and chemical yields, demonstrates its potential as a 'general-purpose' biocatalyst for the production of optically pure oxygenated compounds.Two other promising ethene-utilizing bacteria (M26, M93 A) each catalyzed the stereospecific formation of S-(+)-phenyl glycidyl ether (ee=93%). This has attracted considerable industrial interest and is currently under investigation at ICI for commercial production of optically active./1-blockers. In addition to Micrococcus sp. M90C, the substrate specificities of 6 other organisms were studied in order to probe the active site of the enzymes involved. The pattern of reactivity for the group of 4 ethene-(M26, M90C, M93A, M186) and 2 propene-(M142, M l 56) utilizers differed from that expected with peracids, suggesting a considerable degree of enzymatic control.The nature of the substrate, however, modulated enzymatic epoxidations in Staphylcoccus sp. M97B. CONTENTS

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Stereoselective formation of aromatic sulphoxides by oxidation of sulphides and sulphoxides in the presence of bovine serum albumin

Cited by 18 publications

References 0 publications

Artificial Metalloenzymes: Reaction Scope and Optimization Strategies

Artificial Metalloenzymes: Reaction Scope and Optimization Strategies

Albumin as a promiscuous biocatalyst in organic synthesis

Biocatalysts for production of chiral epoxides

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