Enzymatic Resolution, Desymmetrization, and Dynamic Kinetic Asymmetric Transformation of 1,3-Cycloalkanediols

Fransson, Ann‐Britt L.; Xu, Yongmei; Leijondahl, Karin; Bäckvall, Jan‐Erling

doi:10.1021/jo060002n

Cited by 71 publications

(41 citation statements)

References 26 publications

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“…An efficient DYKAT of a racemic cis/trans mixture of cyclohexane-1,3-diol using Shvo's complex 1 was reported in 2006 [85]. Pseudomonas cepacia lipase (PS-C) was used for the enzymatic resolution along with para-chlorophenyl acetate as the acyl donor.…”

Section: Dykat Of Diolsmentioning

confidence: 99%

Shvo’s Catalyst in Hydrogen Transfer Reactions

Warner

Casey

Bäckvall

2011

Bifunctional Molecular Catalysis

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This chapter reviews the use of Shvo's catalyst in various hydrogen transfer reactions and also discusses the mechanism of the hydrogen transfer. The Shvo catalyst is very mild to use since no activation by base is required in the transfer hydrogenation of ketones or imines or in the transfer dehydrogenation of alcohols and amines. The Shvo catalyst has also been used as an efficient racemization catalyst for alcohols and amines. Many applications of the racemization reaction are found in the combination with enzymatic resolution leading to a dynamic kinetic resolution (DKR). In these dynamic resolutions, the yield based on the starting material can theoretically reach 100%. The mechanism of the hydrogen transfer from the Shvo catalyst to ketones (aldehydes) and imines as well as the dehydrogenation of alcohols and amines has been studied in detail over the past decade. It has been found that for ketones (aldehydes) and alcohols, there is a concerted transfer of the two hydrogens involved, whereas for typical amines and imines, there is a stepwise transfer of the two hydrogens. One important question is whether the substrate is coordinated to the metal or not in the hydrogen transfer step(s). The pathway involving coordination to activate the substrate is called the inner-sphere mechanism, whereas transfer of hydrogen without coordination is called the outer-sphere mechanism. These mechanistic proposals together with experimental and theoretical studies are discussed.

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Section: Dykat Of Diolsmentioning

confidence: 99%

Shvo’s Catalyst in Hydrogen Transfer Reactions

Warner

Casey

Bäckvall

2011

Bifunctional Molecular Catalysis

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“…The extracellular lipase of Candida antarctica, lipase B (CALB), which is an efficient catalyst of hydrolysis, esterification and transesterification reactions, has been used in the alcoholysis of oils, for example in the production of biodiesel (Torres et al 2004;Modi et al 2006), the synthesis of short-chain flavor esters (Larios et al 2004;Han et al 2009), and for kinetic resolution (Fransson et al 2006;Lou and Zong 2006). However, the high cost of the enzyme is a limiting factor.…”

Section: Introductionmentioning

confidence: 99%

Surface display of active lipase in Pichia pastoris using Sed1 as an anchor protein

Zhang

Lin

2010

Biotechnol Lett

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A Pichia pastoris cell-surface display system was constructed using the Sed1 anchor system that has been developed in Saccharomyces cerevisiae. Candida antarctica lipase B (CALB) was used as the model protein and was fused to an anchor that consisted of 338 amino acids of Sed1. The resulting fusion protein CALBSed1 was expressed under the control of the alcohol oxidase 1 promoter (pAOX1). Immunofluorescence microscopy of immunolabeled Pichia pastoris revealed that CALB was displayed on the cell surface. Western blot analysis showed that the fusion protein CALBSed1 was attached covalently to the cell wall and was highly glycosylated. The hydrolytic activity of the displayed CALB was more than 220 U/g dry cells after 120 h of culture. The displayed protein also exhibited a higher degree of thermostability than free CALB.

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“…The DYKAT of cyclic diols has been less studied and previous attempts to obtain enantiomerically pure diol diacetates from 1,3-cyclohexanediol were moderately successful. [10] It occurred to us that bicyclic diols 1 may be more suitable substrates for enzymatic transesterification, and we therefore decided to study them in DYKAT reactions.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Synthesis of Bicyclic Diol Derivatives through Metal and Enzyme Catalysis: Application to the Formal Synthesis of Sertraline

Krumlinde

Bogár

Bäckvall

2010

Chemistry A European J

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Enzyme- and ruthenium-catalyzed dynamic kinetic asymmetric transformation (DYKAT) of bicyclic diols to their diacetates was highly enantio- and diastereoselective to give the corresponding diacetates in high yield with high enantioselectivity (99.9 % ee). The enantiomerically pure diols are accessible by simple hydrolysis (NaOH, MeOH), but an alternative enzyme-catalyzed ester cleavage was also used to give the trans-diol (R,R)-1 b in extremely high diastereomeric purity (trans/cis=99.9:0.1, >99.9 % ee). It was demonstrated that the diols can be selectively oxidized to the ketoalcohols in a ruthenium-catalyzed Oppenauer-type reaction. A formal enantioselective synthesis of sertraline from a simple racemic cis/trans diol 1 b was demonstrated.

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Enzymatic Resolution, Desymmetrization, and Dynamic Kinetic Asymmetric Transformation of 1,3-Cycloalkanediols

Cited by 71 publications

References 26 publications

Shvo’s Catalyst in Hydrogen Transfer Reactions

Shvo’s Catalyst in Hydrogen Transfer Reactions

Surface display of active lipase in Pichia pastoris using Sed1 as an anchor protein

Asymmetric Synthesis of Bicyclic Diol Derivatives through Metal and Enzyme Catalysis: Application to the Formal Synthesis of Sertraline

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