Enzyme‐Promoted Desymmetrisation of Prochiral Bis(cyanomethyl) Sulfoxide

Kiełbasiński, P.; Rachwalski, Michał; Mikołajczyk, M.; Szyrej, Małgorzata; Wieczorek, Michał W.; Wijtmans, Roel; Rutjes, Floris P. J. T.

doi:10.1002/adsc.200700033

Cited by 23 publications

(14 citation statements)

References 25 publications

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“…Racemic and prochiral organosulfur and organophosphorus compounds have proved to be good substrates for various types of enzymes and many useful transformations leading to non‐racemic products have been described by us and others 1a. In this way, enantiomerically enriched products were obtained, having a stereogenic centre located either on sulfur,1b,c phosphorus1d or on a carbon atom of an organic substituent 1e…”

Section: Introductionmentioning

confidence: 99%

Enzymatic Synthesis of Enantiopure Precursors of Chiral Bidentate and Tridentate Phosphorus Catalysts

et al. 2011

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Abstract:The Candida antarctica lipase (CAL-B)-catalyzed acetylation of racemic 2-hydroxy-phenylphosphine oxide, performed in diethyl ether, led to kinetic resolution with an unusually high enantioselectivity (E = 3000). The CAL-B-mediated desymmetrization of prochiral bis(2-hydroxymethylphenyl)methylphosphine oxide gave, via its enantioselective monoacetylation, the corresponding monoacetate in 80% yield and with ee > 98%. The latter transformation allowed us to efficiently transform the prochiral substrate into the enantiomerically pure product in one single step. In both cases the stereogenic or prostereogenic phosphorus atom and the reacting hydroxy oxygen are distant from each other by four bonds. The absolute configurations of all the products were determined by a chemical correlation and X-ray analysis. The products will be used as enantiopure substrates in the preparation of a variety of chiral organophosphorus ligands/catalysts for asymmetric synthesis.

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Section: Introductionmentioning

confidence: 99%

Enzymatic Synthesis of Enantiopure Precursors of Chiral Bidentate and Tridentate Phosphorus Catalysts

et al. 2011

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“…6 + iPrBr). [22] Theorizing about the underlying mechanism we wondered whether a similar reaction de- Representative substrates for enzymatic desymmetrizations by acetylation of 1, [16] nitrile hydrolysis of 2, [17] and ester hydrolyses of 3 [18] and 4. [19,20] Scheme 1.…”

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confidence: 99%

“…[15] Figure 1 depicts selected prochiral monosulfoxides, in which the sulfur atom became a stereocenter through enzymatic monofunctionalizations of one of the two side-chain functional groups. [16][17][18][19][20] Recently we desymmetrized the prochiral dibromo alcohol 5 by an asymmetric bromine-magnesium exchange [21] (Scheme 1; ! 6 + iPrBr).…”

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Desymmetrization of Prochiral Diaryl Sulfoxides by an Asymmetric Sulfoxide–Magnesium Exchange

Hampel

Ruppenthal

Sälinger

et al. 2012

Chemistry A European J

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Transparent glass‐ceramics containing Ln3+‐doped YF3 nanocrystals are successfully obtained under adequate thermal treatment of precursor sol–gel glasses for the first time, to the best of our knowledge. Precipitation of YF3 nanocrystals is confirmed by X‐ray diffraction and high‐resolution transmission electron microscopy images. An exhaustive structural analysis is carried out using Eu3+ and Sm3+ as probe ions of the final local environment in the nano‐structured glass–ceramic. Noticeable changes in luminescence spectra, related to relative intensity and Stark structure of band components, along with remarkably different lifetime values, allow us to discern between ions residing in precipitated YF3 nanocrystals and those remaining in a glassy environment. A large fraction of optically active ions is efficiently partitioned into nanocrystals of small size, around 11 nm. Moreover, bright and efficient up‐conversion, including very intense high‐energy emissions in the UV range, due to 4‐ and 5‐infrared photon processes, are achieved in Yb3+–Tm3+ co‐doped samples. Up‐conversion mechanisms are analysed in depth by means of intensity dependence on sensitiser Yb3+ concentration and pump power.

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“…In the frame of the research carried out in our laboratory, enzymes were intensely used for the synthesis of optically active heteroorganic compounds, particularly those containing a stereogenic center located on a heteroatom–phosphorus , or sulfur. , Some time ago, we reported the synthesis of phosphine oxide precursors of chiral bidentate and tridentate phosphorus catalysts via hydrolytic enzyme-promoted kinetic resolution of racemic P -chiral or desymmetrization of P -prochiral phosphine oxides, which allowed us to obtain the desired products in enantiopure forms (Scheme ). For a review see ref .…”

Section: Introductionmentioning

confidence: 99%

Enzymatic Approach to the Synthesis of Enantiomerically Pure Hydroxy Derivatives of 1,3,5-Triaza-7-phosphaadamantane

et al. 2021

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A series of enantiomerically pure derivatives of 6-(1-hydroxyalkyl)-1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane 5 were successfully synthesized for the first time. A series of hydrolytic enzymes was applied in a stereoselective acetylation performed under kinetic resolution conditions. Although the secondary alcohols: α-aryl-hydroxymethyl-PTA (phosphines) 5b–d′ , PTA-oxides 8b–d′ , and PTA-sulfides 9b–d′ were found to be totally unreactive in the presence of all the enzymes and various conditions applied, the primary alcohols, i.e., the hydroxymethyl derivatives PTA oxide 8a and PTA sulfide 9a , were successfully resolved into enantiomers with moderate to good enantioselectivity (up to 95%). The absolute configurations of the products were determined by an X-ray analysis and chemical correlation.

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Enzyme‐Promoted Desymmetrisation of Prochiral Bis(cyanomethyl) Sulfoxide

Abstract: Prochiral bis(cyanomethyl) sulfoxide has been successfully transformed into the corresponding optically active mono amide and mono acid with enantiomeric excesses ranging from low (10 %) to very high (up to 99 %) using a broad spectrum of nitrilehydrolysing enzymes.

Cited by 23 publications

References 25 publications

Enzymatic Synthesis of Enantiopure Precursors of Chiral Bidentate and Tridentate Phosphorus Catalysts

Enzymatic Synthesis of Enantiopure Precursors of Chiral Bidentate and Tridentate Phosphorus Catalysts

Desymmetrization of Prochiral Diaryl Sulfoxides by an Asymmetric Sulfoxide–Magnesium Exchange

Enzymatic Approach to the Synthesis of Enantiomerically Pure Hydroxy Derivatives of 1,3,5-Triaza-7-phosphaadamantane

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