Deoxysugars: Occurrence, Genetics, and Mechanisms of Biosynthesis

Johnson, David A.; Liu, Hung‐wen

doi:10.1016/b978-0-08-091283-7.00089-8

Cited by 35 publications

(41 citation statements)

References 425 publications

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“…Most naturally occurring deoxyhexoses are deoxygenated at the C6 position; however, further deoxygention at C2, C3 and C4 is also observed [3,6,59]. Although the 2,6-dideoxyhexoses are by far the most abundant deoxy sugars found in natural products, deoxy sugars featuring different patterns of deoxygenation, e.g., 3,6-dideoxy hexoses, are commonly found as components of Gram negative lipopolysaccharide (LPS) O -antigens, where their structural variety contributes to their complex roles in cellular recognition and virulence [60,61].…”

Section: Deoxygenationmentioning

confidence: 99%

“…Consequently, enzymes catalyzing carbon-carbon bond formation can be valuable, especially in the formation of novel branched deoxysugars [98–101]. Branched-chain sugars [3,11,102] are frequently employed in bacterial cell wall formation, where they serve structural roles or contribute to antigenic determinants [61]. In deoxy sugar combinatorial biosynthesis, enzymes capable of branching could allow access to more complex carbohydrates [103].…”

Section: Glycine Additionmentioning

confidence: 99%

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Mechanisms and structures of vitamin B6-dependent enzymes involved in deoxy sugar biosynthesis

Romo

Liu²

2011

Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics

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PLP is well-regarded for its role as a coenzyme in a number of diverse enzymatic reactions. Transamination, deoxygenation, and aldol reactions mediated by PLP-dependent enzymes enliven and enrich deoxy sugar biosynthesis, endowing these compounds with unique structures and contributing to their roles as determinants of biological activity in many natural products. The importance of deoxy amino sugars in natural product biosynthesis has spurred several recent structural investigations of sugar aminotransferases. The structure of a PMP-dependent enzyme catalyzing the C-3 deoxygenation reaction in the biosynthesis of ascarylose was also determined. These studies, and the crystal structures they have provided, offer a wealth of new insights regarding the enzymology of PLP/PMP-dependent enzymes in deoxy sugar biosynthesis. In this review, we consider these recent achievements in the structural biology of deoxy sugar biosynthetic enzymes and the important implications they hold for understanding enzyme catalysis and natural product biosynthesis in general.

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Section: Deoxygenationmentioning

confidence: 99%

Section: Glycine Additionmentioning

confidence: 99%

Mechanisms and structures of vitamin B6-dependent enzymes involved in deoxy sugar biosynthesis

Romo

Liu²

2011

Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics

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“…From these fractions, 23 mg of 90% pure TDP-D-glucose (5) was obtained. 1 TDP-D-glucose (5, 23 mg) obtained from the previous step was dissolved in 47 mM KH 2 PO 4 buffer, pH 7.5, to give a final concentration of 29 μM. This solution was incubated with TDP-D-glucose 4,6-dehydratase (RfbB) from S. enterica LT2 (18 μM) at 37 °C for 2 h, after which RfbB was removed by filtration through an Amicon YM-10 membrane.…”

Section: Enzymatic Synthesis Of Tdp-4-keto-6-deoxy-d-glucose (6)mentioning

confidence: 99%

“…Those fractions containing pure TDP-4-keto-6-deoxy-D-glucose (6, 12.3 mg, >90% purity) were combined and the concentration of 6 in the solution was determined spectrophotometrically at 267 nm, (ε =9600 M −1 cm −1 ). 1…”

Section: Enzymatic Synthesis Of Tdp-4-keto-6-deoxy-d-glucose (6)mentioning

confidence: 99%

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Characterization of TDP-4-Keto-6-deoxy-d-glucose-3,4-ketoisomerase from the d-Mycaminose Biosynthetic Pathway of Streptomyces fradiae: In Vitro Activity and Substrate Specificity Studies

et al. 2006

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Deoxysugars are critical structural elements for the bioactivity of many natural products. Ongoing work on elucidating a variety of deoxysugar biosynthetic pathways has paved the way for manipulation of these pathways for the generation of structurally diverse glycosylated natural products. In the course of this work, the biosynthesis of d-mycaminose in the tylosin pathway of Streptomyces fradiae was investigated. Attempts to reconstitute the entire mycaminose biosynthetic machinery in a heterologous host led to the discovery of a previously overlooked gene, tyl1a, encoding an enzyme thought to convert TDP-4-keto-6-deoxy-d-glucose to TDP-3-keto-6-deoxy-d-glucose, a 3,4-ketoisomerization reaction in the pathway. Tyl1a has now been overexpressed, purified, and assayed, and its activity has been verified by product analysis. Incubation of Tyl1a and the C-3 aminotransferase TylB, the next enzyme in the pathway, produced TDP-3-amino-3,6-dideoxy-d-glucose, confirming that these two enzymes act sequentially. Steady state kinetic parameters of the Tyl1a-catalyzed reaction were determined, and the ability of Tyl1a and TylB to process a C-2 deoxygenated substrate and a CDP-linked substrate was also demonstrated. Enzymes catalyzing 3,4-ketoisomerization of hexoses represent a new class of enzymes involved in unusual sugar biosynthesis. The fact that Tyl1a exhibits a relaxed substrate specificity holds potential for future deoxysugar biosynthetic engineering endeavors.

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Insights into the Branched-Chain Formation of Mycarose: Methylation Catalyzed by an (S)-Adenosylmethionine-Dependent Methyltransferase

Chen¹,

Zhao²,

Hallis³

et al. 2001

Angew. Chem.

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Eine C‐Methyltransferase, die am Aufbau von Methylverzweigungen in Zuckern beteiligt ist, wurde erstmals charakterisiert. TylC3, ein (S)‐Adenosylmethylthionin(AdoMet)‐abhängiges Enzym, katalysiert das Anbringen eines Methylsubstituenten [Gl. (1)] bei der Biosynthese von L‐Mycarose, einem unüblichen Zucker, der in Tylosin und als O‐3‐Methylderivat in Erythromycin vorkommt. Die C‐3‐Methylierung verläuft unter Konfigurationsinversion und benötigt keine Cofaktoren. Die Umsatzgeschwindigkeit ist 1.4±0.1 min−1. TDP=Thymidin‐5′‐dihydrogenphosphat.

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Deoxysugars: Occurrence, Genetics, and Mechanisms of Biosynthesis

Cited by 35 publications

References 425 publications

Mechanisms and structures of vitamin B6-dependent enzymes involved in deoxy sugar biosynthesis

Mechanisms and structures of vitamin B6-dependent enzymes involved in deoxy sugar biosynthesis

Characterization of TDP-4-Keto-6-deoxy-d-glucose-3,4-ketoisomerase from the d-Mycaminose Biosynthetic Pathway of Streptomyces fradiae: In Vitro Activity and Substrate Specificity Studies

Insights into the Branched-Chain Formation of Mycarose: Methylation Catalyzed by an (S)-Adenosylmethionine-Dependent Methyltransferase

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