Amination of benzylic and cinnamic alcohols via a biocatalytic, aerobic, oxidation–transamination cascade

Fuchs, Michael; Tauber, Katharina; Sattler, Johann H.; Lechner, Horst; Pfeffer, Jan; Kroutil, Wolfgang; Faber, Kurt

doi:10.1039/c2ra20800h

Cited by 58 publications

(61 citation statements)

References 35 publications

(9 reference statements)

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“…2), for example, transamination to form primary amines (64,65), hydrocyanation to form chiral cyanohydrins (66), Henry reactions to form nitroalcohols (67), BaeyerVillager oxidation to form esters (68), and Mannich reactions to form ␤-amino-carbonyl compounds (69,70). Some of the aforementioned reactions have already been demonstrated to be functional in a cellular context using resting E. coli cells (66,71).…”

Section: Enhancing Bioconversion Of Aldehydes To Other Chemical Classesmentioning

confidence: 99%

Microbial Engineering for Aldehyde Synthesis

Kunjapur

Prather

2015

Appl Environ Microbiol

138

129

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Aldehydes are a class of chemicals with many industrial uses. Several aldehydes are responsible for flavors and fragrances present in plants, but aldehydes are not known to accumulate in most natural microorganisms. In many cases, microbial production of aldehydes presents an attractive alternative to extraction from plants or chemical synthesis. During the past 2 decades, a variety of aldehyde biosynthetic enzymes have undergone detailed characterization. Although metabolic pathways that result in alcohol synthesis via aldehyde intermediates were long known, only recent investigations in model microbes such as Escherichia coli have succeeded in minimizing the rapid endogenous conversion of aldehydes into their corresponding alcohols. Such efforts have provided a foundation for microbial aldehyde synthesis and broader utilization of aldehydes as intermediates for other synthetically challenging biochemical classes. However, aldehyde toxicity imposes a practical limit on achievable aldehyde titers and remains an issue of academic and commercial interest. In this minireview, we summarize published efforts of microbial engineering for aldehyde synthesis, with an emphasis on de novo synthesis, engineered aldehyde accumulation in E. coli, and the challenge of aldehyde toxicity.

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Section: Enhancing Bioconversion Of Aldehydes To Other Chemical Classesmentioning

confidence: 99%

Microbial Engineering for Aldehyde Synthesis

Kunjapur

Prather

2015

Appl Environ Microbiol

138

129

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“…KNK168 ArR (R) [61] Aspergillus terreus AT (R) [62] Giberella zeae GZ (R) [62] Hyphomonas neptunium HN (R) [62] Neosartorya fischeri NF (R) [62] Arthrobacter citreus ArS (S) [63] Bacillus megaterium BM (S) [63] Chromobacterium violaceum CV (S) [63] Ochrobactrum antropi OA (S) [64] Paracoccus dentrificans PD (S) [65] Pseudomonas fluorescens PF (S) [66] Pseudomonas putida KT2440 PP1 (S) [67] Pseudomonas putida KT2440 PP2 (S) [67] Silicibacter pomeroyi SP (S) [68] Vibrio fluvialis VF (S) [66] FULL PAPER asc.wiley-vch.de product with 73% conversion and 92% ee (R). KNK168 ArR (R) [61] Aspergillus terreus AT (R) [62] Giberella zeae GZ (R) [62] Hyphomonas neptunium HN (R) [62] Neosartorya fischeri NF (R) [62] Arthrobacter citreus ArS (S) [63] Bacillus megaterium BM (S) [63] Chromobacterium violaceum CV (S) [63] Ochrobactrum antropi OA (S) [64] Paracoccus dentrificans PD (S) [65] Pseudomonas fluorescens PF (S) [66] Pseudomonas putida KT2440 PP1 (S) [67] Pseudomonas putida KT2440 PP2 (S) [67] Silicibacter pomeroyi SP (S) [68] Vibrio fluvialis VF (S) [66] FULL PAPER asc.wiley-vch.de product with 73% conversion and 92% ee (R).…”

Section: Source Organismmentioning

confidence: 99%

Asymmetric Amination of α‐Chiral Aliphatic Aldehydes via Dynamic Kinetic Resolution to Access Stereocomplementary Brivaracetam and Pregabalin Precursors

et al. 2017

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Over the last decades biocatalysis has emerged as an indispensable and versatile tool for the asymmetric synthesis of active pharmaceutical ingredients (APIs). In this context, especially transaminases (TAs) have been successfully used for the preparation of numerous a-chiral, optically pure amines, serving as important building blocks for APIs. Here we elaborate on the development of transaminases recognizing the a-chiral centre adjacent to an aldehyde moiety with aliphatic residues, opening up concepts for novel synthetic routes to the antiepileptic drugs Brivaracetam and Pregabalin. The transformation proceeded via dynamic kinetic resolution (DKR) based on the bio-induced racemisation of the aldehyde enantiomers, enabling the amination of the racemic substrates with quantitative conversions. Medium, substrate as well as enzyme engineering gave access to both (R)-and (S)-enantiomers of the amine precursors of the stereocomplementary drugs in high optical purity, representing a short route to mentioned APIs.

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“…For example, the diamination of 1,10-decanediol on preparative scale (174 mg substrate) led to 94% conversion and 70% isolated yield. Alternatively, the alcohol can be oxidized by employing an oxidase followed by amination with a ωTA, 40 however, in this case, additional redox reagents are required.…”

Section: Primary Aminesmentioning

confidence: 99%

Asymmetric Preparation of prim-, sec-, and tert-Amines Employing Selected Biocatalysts

Kroutil

Fischereder

Fuchs

et al. 2013

Org. Process Res. Dev.

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115

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This account focuses on the application of ω-transaminases, lyases, and oxidases for the preparation of amines considering mainly work from our own lab. Examples are given to access α-chiral primary amines from the corresponding ketones as well as terminal amines from primary alcohols via a two-step biocascade. 2,6-Disubstituted piperidines, as examples for secondary amines, are prepared by biocatalytical regioselective asymmetric monoamination of designated diketones followed by spontaneous ring closure and a subsequent diastereoselective reduction step. Optically pure tert-amines such as berbines and N-methyl benzylisoquinolines are obtained by kinetic resolution via an enantioselective aerobic oxidative C–C bond formation.

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Amination of benzylic and cinnamic alcohols via a biocatalytic, aerobic, oxidation–transamination cascade

Cited by 58 publications

References 35 publications

Microbial Engineering for Aldehyde Synthesis

Microbial Engineering for Aldehyde Synthesis

Asymmetric Amination of α‐Chiral Aliphatic Aldehydes via Dynamic Kinetic Resolution to Access Stereocomplementary Brivaracetam and Pregabalin Precursors

Asymmetric Preparation of prim-, sec-, and tert-Amines Employing Selected Biocatalysts

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