Approaches based on enzyme mediated kinetic to dynamic kinetic resolutions: A versatile route for chiral intermediates

Kamal, Ähmed; Azhar, M. Ameruddin; Tadiparthi, Krishnaji; Malik, M. Shaheer; Azeeza, Shaik

doi:10.1016/j.ccr.2007.12.010

Cited by 107 publications

(52 citation statements)

References 153 publications

(143 reference statements)

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“…Dynamic kinetic resolution (DKR) involving an in situ racemization of the non-reacting enantiomerp arallel to the enantiomer selective reaction represents away to overcome this limitation. [49][50][51] Thet wo elementary parts of aD KR process (i.e. , kinetic resolution and simultaneous racemization that could consist of numerous other elementary reactions)m ay have different operational optima.…”

Section: Introductionmentioning

confidence: 99%

A Continuous‐Flow Cascade Reactor System for Subtilisin A‐ Catalyzed Dynamic Kinetic Resolution of N‐tert‐Butyloxycarbonylphenylalanine Ethyl Thioester with Benzylamine

et al. 2016

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Alcalase (Subtilisin A) was immobilized by simple hydrophobic adsorption onto various surface-grafted macroporous silicag els resulting in easy-to-prepare and stable biocatalystse nabling the efficient kinetic resolution (KR) and dynamic kinetic resolution (DKR)o fr acemic N-Boc-phenylalanine ethyl thioester with benzylamine.T he immobilized Alcalaseb iocatalysts, which retained their activity and selectivity when stored at 4 8 8Cf or more than ay ear, were testedi ne nzymatic aminolysis in batch and continuous-flow KRs resulting in (S)-N-Bocphenylalanine benzylamide in high enantiomeric purity. In KR of the racemict hioester by Alcalasecatalyzed aminolysis in ac ontinuous-flow reactor, the productivity (specific reactionr ate, r flow )a nd enantiomeric ratio (E)w ere studied in the 0-100 8 8C range.T he effect of the temperature on base-catalyzed racemization of the non-transformed (R)-thioester in ac ontinuous-flow reactor was also investigated in the 0-150 8 8Cr ange.T he continuous-mode DKR of the racemic thioester in as erialc ascade systemo fsix biocatalyst-filled columns at 50 8 8Cf or KR and five grafteds ilica gel-filled columns at 150 8 8Cf or racemization resulted in the formation of the (S)-benzylamide in 79% conversion, 8.17 g L À1 h À1 volumetric productivity and 98% ee. This is the first example of ad ynamic kinetic resolution of an amino acid derivative in continuous-flow mode using an alternating cascade of packed-bed enzyme reactors and racemization reactors kept at different temperatures.

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Section: Introductionmentioning

confidence: 99%

A Continuous‐Flow Cascade Reactor System for Subtilisin A‐ Catalyzed Dynamic Kinetic Resolution of N‐tert‐Butyloxycarbonylphenylalanine Ethyl Thioester with Benzylamine

et al. 2016

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“…In continuation of our earlier efforts towards [56][57][58][59][60][61][62][63][64][65] the synthesis of optically active biologically important compounds using lipase-catalyzed resolution, herein we wish to report the synthesis of (-)-centrolobine (Fig. 1) using this method.…”

Section: Resultsmentioning

confidence: 99%

Lipase-Catalyzed Resolution of 1-[4-(Benzyloxy)phenyl]hex-5-en-3-ol: Synthesis of (-)-Centrolobine

Tadiparthi¹,

Raghavendra²,

Kamal³

2017

Asian J. Chem.

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A practical and efficient method for the preparation of homoallylic alcohol and its successful enzymatic resolution has been developed. This lipase-catalyzed resolution process has been optimized with respect to different lipases and solvents. Moreover, Mitsunobu strategy has been applied to recover the unwanted isomer. Further optically enriched homoallylic alcohol has been employed for the synthesis of (-)-centrolobine.

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“…A vast array of examples of enzymatic kinetic resolution are available in the literature and these have been reviewed in detail. [251][252][253] Figure 12 describes examples of enzymatic kinetic resolution of an achiral substrate by acylation, deacylation, oxidation, and reduction. Figure 12 …”

Section: Figure 11mentioning

confidence: 99%

“…253 Enzymatic dynamic kinetic resolution has been performed with thioesters due to the high acidity of their α-protons (Scheme 10). …”

Section: Figure 14mentioning

confidence: 99%

Recent trends in whole cell and isolated enzymes in enantioselective synthesis

Milner¹,

Maguire²

2012

Arkivoc

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Modern synthetic organic chemistry has experienced an enormous growth in biocatalytic methodologies; enzymatic transformations and whole cell bioconversions have become generally accepted synthetic tools for asymmetric synthesis. This review details an overview of the latest achievements in biocatalytic methodologies for the synthesis of enantiopure compounds with a particular focus on chemoenzymatic synthesis in non-aqueous media, immobilisation technology and dynamic kinetic resolution. Furthermore, recent advances in ketoreductase technology and their applications are also presented.Keywords: Biocatalysis, kinetic and dynamic kinetic resolution, Baker's yeast, ketoreductases General IntroductionAsymmetric synthesis is the preferential formation of one stereoisomer of a chiral target compound to another; when scientists at GlaxoSmithKline, AstraZeneca and Pfizer 1 examined 128 syntheses from their companies, they found as many as half of the drug compounds made by their process research and development groups are not only chiral but also contain an average of two chiral centres each. 2In 2006 just 25 % were derived from the chiral pool and over 50 % employed chiral technologies. 1In order to meet regulatory requirements enantiomeric purities of 99.5 % were deemed necessary by the FDA. 3 This is one of the biggest challenges which face chemists today, primarily due to the recognition of the fact that different enantiomers of the same compound can interact differently in biological systems. As a consequence, the production of single enantiomers instead of racemic mixtures has become an important process in the pharmaceutical and agrochemical industry. Several routes can lead to the desired enantiomer including transition metal-, [4][5][6] organo-5,7-10 and bio-catalysis [11][12][13][14][15] and these have been thoroughly reviewed in the literature. 16,17 2. Biocatalysis IntroductionBiocatalysis involves the use of enzymes or whole cells (containing the desired enzyme or enzyme system) as catalysts for chemical reactions. A timeline of historic events in biocatalysis and biotechnology is outlined in Table 1. [18][19][20] Reviews and Accounts Novel methodologies for discovering industrial enzymes based on genomic sequencing and phage display (discussed further in Section 1.3), 21,22 as well as highly effective optimisation tools based on chemical, physical and molecular biology approaches, 23 have improved the access to biocatalysts, increased their stability, and radically broadened their specificity. 24This greater availability of catalysts with superior qualities including the use of new bioengineering tools contributed significantly to the development of new industrial processes. Biocatalytic methodologies for organic synthesis were outlined by Woodley et al. in three categories: established, emerging and expanding chemistries as depicted in Figure 1. 25 Enzyme classesBy the late 1950s it had become evident that the nomenclature of enzymes without any guiding authority, in a period when the...

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Approaches based on enzyme mediated kinetic to dynamic kinetic resolutions: A versatile route for chiral intermediates

Cited by 107 publications

References 153 publications

A Continuous‐Flow Cascade Reactor System for Subtilisin A‐ Catalyzed Dynamic Kinetic Resolution of N‐tert‐Butyloxycarbonylphenylalanine Ethyl Thioester with Benzylamine

A Continuous‐Flow Cascade Reactor System for Subtilisin A‐ Catalyzed Dynamic Kinetic Resolution of N‐tert‐Butyloxycarbonylphenylalanine Ethyl Thioester with Benzylamine

Lipase-Catalyzed Resolution of 1-[4-(Benzyloxy)phenyl]hex-5-en-3-ol: Synthesis of (-)-Centrolobine

Recent trends in whole cell and isolated enzymes in enantioselective synthesis

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