Asymmetric synthesis of 1,3-oxathiolan-5-one derivatives through dynamic covalent kinetic resolution

Zhang, Yan; Schaufelberger, Fredrik; Sakulsombat, Morakot; Liu, Chelsea; Ramström, Olof

doi:10.1016/j.tet.2014.03.059

Cited by 35 publications

(24 citation statements)

References 37 publications

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“…[19] Oxidative kinetic resolutions have in most cases been applied to racemic alcohols. [20][21][22] Conventionally,k inetic resolutions are performed with hydrolases, [23][24][25][26][27][28] because of their simple handling without the need for cofactor regeneration systems. In addition to these, the described kinetic resolution of the hydroxy ketone rac-1 (Scheme 1) represents am eans of biocatalytic access to enantiomerically pure tertiary alcohols throught he use of dehydrogenases.…”

Section: Discussionmentioning

confidence: 99%

Screening, Molecular Cloning, and Biochemical Characterization of an Alcohol Dehydrogenase from Pichia pastoris Useful for the Kinetic Resolution of a Racemic β‐Hydroxy‐β‐trifluoromethyl Ketone

et al. 2016

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The stereoselective synthesis of chiral 1,3-diols with the aid of biocatalysts is an attractive tool in organic chemistry. Besides the reduction of diketones, an alternative approach consists of the stereoselective reduction of β-hydroxy ketones (aldols). Thus, we screened for an alcohol dehydrogenase (ADH) that would selectively reduce a β-hydroxy-β-trifluoromethyl ketone. One potential starting material for this process is readily available by aldol addition of acetone to 2,2,2-trifluoroacetophenone. Over 200 strains were screened, and only a few yeast strains showed stereoselective reduction activities. The enzyme responsible for the reduction of the β-hydroxy-β-trifluoromethyl ketone was identified after purification and subsequent MALDI-TOF mass spectrometric analysis. As a result, a new NADP(+) -dependent ADH from Pichia pastoris (PPADH) was identified and confirmed to be capable of stereospecific and diastereoselective reduction of the β-hydroxy-β-trifluoromethyl ketone to its corresponding 1,3-diol. The gene encoding PPADH was cloned and heterologously expressed in Escherichia coli BL21(DE3). To determine the influence of an N- or C-terminal His-tag fusion, three different recombinant plasmids were constructed. Interestingly, the variant with the N-terminal His-tag showed the highest activity; consequently, this variant was purified and characterized. Kinetic parameters and the dependency of activity on pH and temperature were determined. PPADH shows a substrate preference for the reduction of linear and branched aliphatic aldehydes. Surprisingly, the enzyme shows no comparable activity towards ketones other than the β-hydroxy-β-trifluoromethyl ketone.

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Section: Discussionmentioning

confidence: 99%

Screening, Molecular Cloning, and Biochemical Characterization of an Alcohol Dehydrogenase from Pichia pastoris Useful for the Kinetic Resolution of a Racemic β‐Hydroxy‐β‐trifluoromethyl Ketone

et al. 2016

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“…温度才能进行, 相应地, 可得到多种手性吡咯酮化合物(图6A) [34,35] . 另一方面, 硫代半缩醛反应因为巯基的高亲核性, 也能在常温条件下实现对羰基的快速加成 [36] , 并连接酶不对称催化, 可获得1,3-氧硫环戊烷母核(12, 15, 图6B和C), 而该类结构是合成抗艾滋病药物拉米夫定(Lamivudine)的重要中间体 [26,37,38] . [39,40] .…”

Section: 与半缩醛相比半胺醛反应的可逆性需要较高的unclassified

Dynamic covalent chemistry in enzyme catalysis

Zhang¹,

Chen²

2019

Sci. Sin.-Vitae

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Bioorthogonal chemistry: a covalent strategy for the study of biological systems SCIENCE CHINA Chemistry 53, 61 (2010); Understanding enzyme catalysis by means of supramolecular artificial enzymes SCIENCE CHINA Chemistry 56, 1067 (2013); High-contrast flicker luminescence on dynamic covalent structure based nanoaggregates SCIENCE CHINA Chemistry 62, 220 (2019); Dynamic separation of Xe and Kr by metal-organic framework and covalent-organic materials: a comparison with activated charcoal

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“…Ramström and co-workers recently reported asymmetric synthesis of 1,3-oxanthiolan-5-one derivatives [48] and oxathiazinanones [49] through dynamic covalent kinetic resolution. In the first case, dynamic hemithioacetal formation combined with intramolecular, CALB-catalyzed lactonization resulted in the final product in good conversion with moderate to good enantiomeric excess (ee) (Scheme 4A).…”

Section: Other Tandem Reactions By Transition Metal Catalysts and Lipmentioning

confidence: 99%

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

Wang

Zhao

2016

Catalysts

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Abstract:The application of biocatalysts in the synthesis of fine chemicals and medicinal compounds has grown significantly in recent years. Particularly, there is a growing interest in the development of one-pot tandem catalytic systems combining the reactivity of a chemical catalyst with the selectivity engendered by the active site of an enzyme. Such tandem catalytic systems can achieve levels of chemo-, regio-, and stereo-selectivities that are unattainable with a small molecule catalyst. In addition, artificial metalloenzymes widen the range of reactivities and catalyzed reactions that are potentially employable. This review highlights some of the recent examples in the past three years that combined transition metal catalysis with enzymatic catalysis. This field is still in its infancy. However, with recent advances in protein engineering, catalyst synthesis, artificial metalloenzymes and supramolecular assembly, there is great potential to develop more sophisticated tandem chemoenzymatic processes for the synthesis of structurally complex chemicals.

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Asymmetric synthesis of 1,3-oxathiolan-5-one derivatives through dynamic covalent kinetic resolution

Cited by 35 publications

References 37 publications

Screening, Molecular Cloning, and Biochemical Characterization of an Alcohol Dehydrogenase from Pichia pastoris Useful for the Kinetic Resolution of a Racemic β‐Hydroxy‐β‐trifluoromethyl Ketone

Screening, Molecular Cloning, and Biochemical Characterization of an Alcohol Dehydrogenase from Pichia pastoris Useful for the Kinetic Resolution of a Racemic β‐Hydroxy‐β‐trifluoromethyl Ketone

Dynamic covalent chemistry in enzyme catalysis

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

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