Chemoenzymatic Access to Chiral Tetrols Produced by Thiamine Diphosphate Dependent Benzaldehyde Lyase

Zecevic, Damir; Germer, Philipp; Walter, Lydia; Gauchenova, Ekaterina; Müller, Michael

doi:10.1002/ejoc.201800980

Cited by 4 publications

(3 citation statements)

References 42 publications

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“…Previously, we have shown that BAL ligates benzaldehyde and acetonide‐protected glyceraldehyde . The latter can be obtained by performing a formyl elongation of the 2‐hydroxy aldehyde glycolaldehyde with KdcA and thus could be used for the biocatalytic formation of enantiopure building blocks such as (1 S ,2 S ,3 R )‐1‐phenylbutane‐1,2,3,4‐tetrol . Aldolases are also known to convert hydroxy aldehydes for the synthesis of highly functionalised polyols and might be used in bienzymatic cascades with KdcA…”

Section: Methodsmentioning

confidence: 99%

Thiamine Diphosphate Dependent KdcA‐Catalysed Formyl Elongation of Aldehydes

et al. 2019

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The formose reaction, one of the oldest name reactions in organic chemistry, uses formaldehyde as a C1 unit resulting in different monosaccharides and sugar‐like compounds. Nucleophilic formyl elongation is an attractive option to obtain 1,2‐functionalised building blocks for organic synthesis and pharmaceuticals; however, it has rarely been applied in asymmetric catalysis. The thiamine diphosphate dependent enzyme 2‐keto acid decarboxylase (KdcA) from Lactococcus lactis is able to transfer formyl units to aliphatic and aromatic aldehydes, both in an electrophilic and in a nucleophilic way. We have established the formation of unstable chiral 2‐hydroxy aldehydes by subsequent modifications (chemical derivatisation with 2,4‐dinitrophenylhydrazine, (R)‐Mosher's acid chloride) or by enzymatic trapping (oxidation and reductive amination).

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Section: Methodsmentioning

confidence: 99%

Thiamine Diphosphate Dependent KdcA‐Catalysed Formyl Elongation of Aldehydes

et al. 2019

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“…Acetonide-protected glyceraldehyde, the product of FSA and KdcA, is a valuable building block for the synthesis of stereoenriched polyols such as (1S,2S,3R)-1-phenylbutane-1,2,3,4-tetrol. 200 In 2017, a cascade with ThDP-dependent FLS and aldolase FSA to generate chiral carbohydrates was outlined, which illustrates the great potential of this kind of enzyme combination. 201 The high reactivity of formaldehyde can also result in nonenzymatic reactions in the biochemical environment.…”

Section: Review Synthesismentioning

confidence: 99%

Biocatalytic One-Carbon Transfer – A Review

Müller¹,

Germer²,

Andexer³

2022

Synthesis

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This review provides an overview of different C1 building blocks as substrates of enzymes, or part of their cofactors, and the resulting functionalized products. There is an emphasis on the broad range of possibilities of biocatalytic one-carbon extensions with C1 sources of different oxidation states. The identification of uncommon biosynthetic strategies, many of which might serve as templates for synthetic or biotechnological applications, towards one-carbon extensions is supported by recent genomic and metabolomic progress and hence we refer principally to literature spanning from 2014 to 2020.1 Introduction2 Methane, Methanol, and Methylamine3 Glycine4 Nitromethane5 SAM and SAM Ylide6 Other C1 Building Blocks7 Formaldehyde and Glyoxylate as Formaldehyde Equivalents8 Cyanide9 Formic Acid10 Formyl-CoA and Oxalyl-CoA11 Carbon Monoxide12 Carbon Dioxide13 Conclusions

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“…Moreover, 1,4-diketones have been shown to be useful building blocks for the preparation of cyclopentenones and five-membered heterocycles, which are found in numerous natural products . Several methods for the synthesis of γ-diketones have been described, − but many are neither generalizable nor convenient, are not ecofriendly, and show poor stereoselectivity. Thus, a practical and stereoselective reaction that operates under mild conditions is obviously highly desirable.…”

mentioning

confidence: 99%

Achiral Hydroxypyruvaldehyde Phosphate as a Platform for Multi-Aldolases Cascade Synthesis of Diuloses and for a Quadruple Acetaldehyde Addition Catalyzed by 2-Deoxyribose-5-Phosphate Aldolases

et al. 2019

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The 1,4-dicarbonyl unit is found in numerous molecules of biological interest, many of which are also polyhydroxylated. We developed a general, one-pot, multistep, stereoselective enzymatic method to prepare diuloses of structural diversity from achiral hydroxypyruvaldehyde phosphate (HPP) as the common electrophile for various aldolases. Surprisingly, for 2-deoxyribose-5-phosphate aldolases, HPP was an acceptor of choice for the multiple addition of acetaldehyde, widening the scope of longer-chain aldol adducts.

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Chemoenzymatic Access to Chiral Tetrols Produced by Thiamine Diphosphate Dependent Benzaldehyde Lyase

Cited by 4 publications

References 42 publications

Thiamine Diphosphate Dependent KdcA‐Catalysed Formyl Elongation of Aldehydes

Thiamine Diphosphate Dependent KdcA‐Catalysed Formyl Elongation of Aldehydes

Biocatalytic One-Carbon Transfer – A Review

Achiral Hydroxypyruvaldehyde Phosphate as a Platform for Multi-Aldolases Cascade Synthesis of Diuloses and for a Quadruple Acetaldehyde Addition Catalyzed by 2-Deoxyribose-5-Phosphate Aldolases

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