Chemo-enzymatic deracemization methods for the preparation of enantiopure non-natural α-amino acids

Servi, Stefano De; Tessaro, Davide; Pedrocchi-Fantoni, Giuseppe

doi:10.1016/j.ccr.2007.09.012

Cited by 91 publications

(41 citation statements)

References 79 publications

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“…The synthesis of this class of amino acids is still a challenge for organic chemists. [14] Many enzymatic approaches have been exploited for their preparation including (i) deracemization [15] or kinetic resolution of chemically modified forms of racemic amino acids [16] using amidases, [17] hydantoinases, [18] and acylases; [19] and (ii) stereoselective synthesis of enantiopure amino acids from oxo acids [20] using dehydrogenases [21] and transaminases.…”

Section: Conversion Of (S)-α-chloro-β-arylpropionic Acids Into Psubstmentioning

confidence: 99%

Biocatalyzed Enantioselective Reduction of Activated C=C Bonds: Synthesis of Enantiomerically Enriched α‐Halo‐β‐arylpropionic Acids

et al. 2011

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The enantioselective biocatalyzed reduction of the C=C bond of some (Z)‐methyl α‐halo‐β‐arylacrylates was investigated. The reaction was performed by baker's yeast fermentation and Old Yellow Enzymes 1–3 mediated biotransformations. The final products were, respectively, enantiomerically enriched (S)‐α‐halo‐β‐arylpropionic acids and their methyl esters, and ester hydrolysis was promoted in the whole cell system. High conversions and enantioselectivity values were observed when the aromatic ring was substituted by an electron‐withdrawing group. Further manipulation of two of these enantiomerically enriched (S)‐haloacids afforded p‐substituted D‐phenylalanines.

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Section: Conversion Of (S)-α-chloro-β-arylpropionic Acids Into Psubstmentioning

confidence: 99%

Biocatalyzed Enantioselective Reduction of Activated C=C Bonds: Synthesis of Enantiomerically Enriched α‐Halo‐β‐arylpropionic Acids

et al. 2011

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“…L-phenylglycine (38a) was also obtained in an eight-step cascade starting from L-phenylalanine (19), which was transformed to (S)-mandelic acid (25) as shown in Scheme 6, followed by further conversion into 38a by the sequence described in the previous paragraph [50]. Transformation of 40 mM of (S)-L-phenylalanine with E. coli cells co-expressing all required enzymes afforded L-phenylglycine with 85% conversion and 99% ee within 24 h. The challenging eight-step biocatalytic cascade was successfully achieved with a single recombinant strain co-expressing 10 enzymes.…”

Section: α-And β-Amino Acidsmentioning

confidence: 99%

Artificial Biocatalytic Linear Cascades to Access Hydroxy Acids, Lactones, and α- and β-Amino Acids

2018

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α-, β-, and ω-Hydroxy acids, amino acids, and lactones represent common building blocks and intermediates for various target molecules. This review summarizes artificial cascades published during the last 10 years leading to these products. Renewables as well as compounds originating from fossil resources have been employed as starting material. The review provides an inspiration for new cascade designs and may be the basis to design variations of these cascades starting either from alternative substrates or extending them to even more sophisticated products.

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“…[12] Various methods for the preparation of enantiopure non-natural aamino acids have been reported. [11] The aim of the concept presented in this paper is to transform the a-hydroxy acid mandelic acid 1 into the corresponding optically pure non-natural a-amino acid. In a first step the a-hydroxy acid should be oxidised to the corresponding a-oxo acid (Scheme 1); the latter should concurrently be transformed to the corresponding a-amino acid via an asymmetric reductive amination, whereby the formal hydrogen abstracted in the oxidation is used in the reduction; therefore both reactions -the enantioselective oxidation as well as the stereoselective reduction -have to run simultaneously.…”

mentioning

confidence: 99%

“…For example, d-phenylglycine or d-4-hydroxyphenylglycine are used as building blocks for semi-synthetic broadspectrum antibiotics like Ampicillin and Amoxicillin. [11] Other non-natural amino acids are needed as templates in asymmetric synthesis. [12] Various methods for the preparation of enantiopure non-natural aamino acids have been reported.…”

mentioning

confidence: 99%

Deracemisation of Mandelic Acid to Optically Pure Non‐Natural L‐Phenylglycine via a Redox‐Neutral Biocatalytic Cascade

2010

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A biocatalytic redox-neutral reaction cascade was designed for the deracemisation of racemic mandelic acid to yield optically pure l-phenylglycine employing three enzymes. The cascade consisted of three steps: a racemisation, an enantioselective oxidation and a stereoselective reductive amination. The enantioselective oxidation of dmandelic acid to the corresponding oxo acid was coupled with the stereoselective reductive amination of the latter; thus the oxidation as well as the reduction reactions were performed simultaneously. The formal hydrogen abstracted in the first stepthe oxidation -was consumed in the reductive amination allowing a redox-neutral cascade due to a cascade-internal cofactor recycling. The enantiomers of the starting material were interconverted by a racemase (mandelate racemase) ensuring that in theory 100% of the starting material can be transformed. Using this set-up racemic mandelic acid was transformed to optically pure l-phenylglycine (ee > 97%) at 94% conversion without the requirement of any additional redox reagents in stoichiometric amounts.

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Chemo-enzymatic deracemization methods for the preparation of enantiopure non-natural α-amino acids

Cited by 91 publications

References 79 publications

Biocatalyzed Enantioselective Reduction of Activated C=C Bonds: Synthesis of Enantiomerically Enriched α‐Halo‐β‐arylpropionic Acids

Biocatalyzed Enantioselective Reduction of Activated C=C Bonds: Synthesis of Enantiomerically Enriched α‐Halo‐β‐arylpropionic Acids

Artificial Biocatalytic Linear Cascades to Access Hydroxy Acids, Lactones, and α- and β-Amino Acids

Deracemisation of Mandelic Acid to Optically Pure Non‐Natural L‐Phenylglycine via a Redox‐Neutral Biocatalytic Cascade

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