Non‐Oxidative Enzymatic (De)Carboxylation of (Hetero)Aromatics and Acrylic Acid Derivatives

The utilization of carbon dioxide as a C1‐building block for the production of valuable chemicals has recently attracted much interest. Whereas chemical CO2 fixation is dominated by C−O and C−N bond forming reactions, the development of novel concepts for the carboxylation of C‐nucleophiles, which l...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2019-06, Vol.361 (11), p.2402-2420
Main Authors: Payer, Stefan E., Faber, Kurt, Glueck, Silvia M.
Format: Article
Language:English
Subjects:
(de)carboxylation
Acids
Acrylic acid
Benzoic acid
Bicarbonates
biocatalysis
Biotransformation
Carbon dioxide
Carboxylation
Carboxylic acids
Catalysis
CO2 fixation
decarboxylases
Decarboxylation
Derivatives
Enzymes
Nucleophiles
Organic chemistry
Phenolic acids
Phenols
reaction mechanisms
Review
Reviews
substrate scope
Substrates
Transition metals
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Summary:The utilization of carbon dioxide as a C1‐building block for the production of valuable chemicals has recently attracted much interest. Whereas chemical CO2 fixation is dominated by C−O and C−N bond forming reactions, the development of novel concepts for the carboxylation of C‐nucleophiles, which leads to the formation of carboxylic acids, is highly desired. Beside transition metal catalysis, biocatalysis has emerged as an attractive method for the highly regioselective (de)carboxylation of electron‐rich (hetero)aromatics, which has been recently further expanded to include conjugated α,β‐unsaturated (acrylic) acid derivatives. Depending on the type of substrate, different classes of enzymes have been explored for (i) the ortho‐carboxylation of phenols catalyzed by metal‐dependent ortho‐benzoic acid decarboxylases and (ii) the side‐chain carboxylation of para‐hydroxystyrenes mediated by metal‐independent phenolic acid decarboxylases. Just recently, the portfolio of bio‐carboxylation reactions was complemented by (iii) the para‐carboxylation of phenols and the decarboxylation of electron‐rich heterocyclic and acrylic acid derivatives mediated by prenylated FMN‐dependent decarboxylases, which is the main focus of this review. Bio(de)carboxylation processes proceed under physiological reaction conditions employing bicarbonate or (pressurized) CO2 when running in the energetically uphill carboxylation direction. Aiming to facilitate the application of these enzymes in preparative‐scale biotransformations, their catalytic mechanism and substrate scope are analyzed in this review.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.201900275