Sequential biocatalytic kinetic resolutions

Guo, Zhiwei; Wu, Shih Hsiung; Chen, Ching Shih; Girdaukas, Gary; Sih, Charles J.

doi:10.1021/ja00168a046

Cited by 98 publications

(11 citation statements)

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“…The phenomenon that diols are inferior substrates than their corresponding monoacylated derivatives in lipase catalyzed transesterification is generally known. It was also observed for racemic diols with C2 symmetry [ 26 , 27 ] where the first acylation step is less enantioselective than the second one. An analogous behavior was found for many prochiral diols [ 28 , 29 , 30 , 31 ] in which the monoacylation step shows a low or only moderate enantioselectivity, but in many cases the low enantioselectivity can be overcome by application of a sequential lipase-catalyzed acylation procedure [ 22 ].…”

Section: Resultsmentioning

confidence: 92%

Lipases as Tools in the Synthesis of Prodrugs from Racemic 9-(2,3-Dihydroxypropyl)adenine

et al. 2012

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Lipases from Geotrichum candidum 4013 (extracellular lipase and cell-bound lipase) were immobilized by adsorption on chitosan beads. The enzyme preparations were tested in the synthesis of ester prodrugs from racemic 9-(2,3-dihydroxypropyl)adenine in dimethylformamide with different vinyl esters (acetate, butyrate, decanoate, laurate, palmitate). The transesterification activities of these immobilized enzymes were compared with commercially available lipases (lipase from hog pancreas, Aspergillus niger, Candida antarctica, Pseudomonas fluorescens). Lipase from Candida antarctica was found to be the most efficient enzyme regarding chemical yield of the desired products, while transesterification by lipase from Aspergillus niger resulted in lower yields.

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Section: Resultsmentioning

confidence: 92%

Lipases as Tools in the Synthesis of Prodrugs from Racemic 9-(2,3-Dihydroxypropyl)adenine

et al. 2012

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“…To date, numerous publications for the stereoselective synthesis of 1,3-diols that contain two stereogenic centers and important interemediate for various purposes have been reported [1,47], involving asymmetric homogeneous and heterogeneous hydrogenation and diastereoselective reduction [48], radical chain elongation [49], enzymatic and non-enzymatic asymmetrization [50,51], dynamic kinetic resolution [52], and stereoselective aldol-Tishchenko reactions [53]. However, there is still substantial demand for stereoselective synthetic methods to produce all possible stereoisomers of chiral 1,3-diols.…”

Section: Resultsmentioning

confidence: 99%

Design and Synthesis of Chiral Zn2+ Complexes Mimicking Natural Aldolases for Catalytic C–C Bond Forming Reactions in Aqueous Solution

Itoh

Sonoike

Kitamura

et al. 2014

IJMS

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Extending carbon frameworks via a series of C–C bond forming reactions is essential for the synthesis of natural products, pharmaceutically active compounds, active agrochemical ingredients, and a variety of functional materials. The application of stereoselective C–C bond forming reactions to the one-pot synthesis of biorelevant compounds is now emerging as a challenging and powerful strategy for improving the efficiency of a chemical reaction, in which some of the reactants are subjected to successive chemical reactions in just one reactor. However, organic reactions are generally conducted in organic solvents, as many organic molecules, reagents, and intermediates are not stable or soluble in water. In contrast, enzymatic reactions in living systems proceed in aqueous solvents, as most of enzymes generally function only within a narrow range of temperature and pH and are not so stable in less polar organic environments, which makes it difficult to conduct chemoenzymatic reactions in organic solvents. In this review, we describe the design and synthesis of chiral metal complexes with Zn2+ ions as a catalytic factor that mimic aldolases in stereoselective C–C bond forming reactions, especially for enantioselective aldol reactions. Their application to chemoenzymatic reactions in aqueous solution is also presented.

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“…In the sequential enantioselective hydrolysis of diacetoxy 1,l '-bi-2-naphthyl (Wu et al, 1985) and in the two-step lipase catalyzed esterification of 2,4-pentanediols (Guo et al, 1990) optical purities of the compound of interest were not much higher than expected from the single step resolution. This inefficiency can be explained by the big difference in the reaction rates of the two subsequent steps: It was modeled and quantitatively shown in simulation by Straathof, Rakels and Heijnen (1990) and suggested from experimental results by Macfarlane, Roberts and Turner (1 990) that both rates must be of the same order of magnitude for optimal results.…”

Section: Optimization Of Sequential Kinetic Resolutionmentioning

confidence: 90%

Sequential Kinetic Resolution by two Enantioselective Enzymes

et al. 1994

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Enhancement of the enantioselectivity by simultaneous use of two enzymes in a sequential kinetic resolution process is presented. The model system consisted of carboxylesterase NP catalyzed hydrolysis of racemic methyl 2-chloropropionate, followed by dehalogenation of the enantiomerically enriched 2-chloropropionate by DL-dehalogenase into lactate. Optimal results are shown to be attained when the conversion rates of both faster reacting enantiomers are the same. An optimization parameter D for sequential resolutions is introduced. The kinetics of both reaction steps were investigated separately by progress curve analysis, and the enantioselectivity of the enzymes was determined. From a quantitative kinetic model we could formulate the sequential resolution, which yielded the predicted improvements of product enantiomeric excess.

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Sequential biocatalytic kinetic resolutions

Cited by 98 publications

References 0 publications

Lipases as Tools in the Synthesis of Prodrugs from Racemic 9-(2,3-Dihydroxypropyl)adenine

Lipases as Tools in the Synthesis of Prodrugs from Racemic 9-(2,3-Dihydroxypropyl)adenine

Design and Synthesis of Chiral Zn2+ Complexes Mimicking Natural Aldolases for Catalytic C–C Bond Forming Reactions in Aqueous Solution

Sequential Kinetic Resolution by two Enantioselective Enzymes

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