Unique biocatalytic resolution of racemic tetrahydroberberrubine via kinetic glycosylation and enantio-selective sulfation

Ge, Haixia; Zhang, Jian; Dong, Ying; Cui, Kai; Yu, Boyang

doi:10.1039/c2cc32175k

Cited by 16 publications

(9 citation statements)

References 18 publications

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“…In this study, complete β stereoselectivity and moderate diastereoselectivity were observed. Furthermore, biocatalytic glycosylation resolution of racemic tetrahydroberberrubine was reported by Yu et al 5. While our continuing efforts regarding this issue were unsuccessful, Fairbanks et al.…”

Section: Glycosylation Reaction Of 1 α and (±)‐5 Several Reaction Conmentioning

confidence: 86%

Chiral Brønsted Acid Mediated Glycosylation with Recognition of Alcohol Chirality

et al. 2013

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Süße Katalyse: Bei einer Glykosylierung unter Aktivierung durch das chirale Phosphorsäurederivat 2 reagiert selektiv ein Enantiomer eines racemischen Alkohols mit 1 zum entsprechenden Glykosid, das in guten Ausbeuten und mit guten bis ausgezeichneten α/β‐ und Diastereoselektivitäten erhalten wird. Die Reaktion ermöglichte die Synthese eines chiralen natürlichen Flavanglykosids ausgehend von einem racemischen Aglykon.

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Section: Glycosylation Reaction Of 1 α and (±)‐5 Several Reaction Conmentioning

confidence: 86%

Chiral Brønsted Acid Mediated Glycosylation with Recognition of Alcohol Chirality

et al. 2013

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“…[4] In this study, complete b stereoselectivity and moderate diastereoselectivity were observed. Furthermore, biocatalytic glycosylation resolution of racemic tetrahydroberberrubine was reported by Yu et al [5] While our continuing efforts regarding this issue were unsuccessful, Fairbanks et al recently reported a/bstereoselective glycosylation of a galactosyl trichloroacetimidate and chiral alcohols using a chiral Brønsted acid. [6,7] In that study, high b stereoselectivity, induced by a chiral Brønsted acid, was demonstrated.…”

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confidence: 96%

Chiral Brønsted Acid Mediated Glycosylation with Recognition of Alcohol Chirality

et al. 2013

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Many carbohydrate-containing natural products, which possess mono-and oligosaccharides, such as proteoglycans, glycoproteins, glycolipids, and antibiotics, are found in nature as important biological substances. A large number of recent biological studies on these glycomolecules at the molecular level have shed light on the biological significance of their carbohydrate units (glycons) in molecular recognition for the transmission of biological information. [1] It is now recognized that carbohydrates are at the heart of a multitude of biological events. [1] Additionally, some glycomolecules have been developed as new functional materials. [2] For example, certain alkyl glycosides are expected to be biodegradable surfactants. Therefore, glycomolecules continue to be the central focus of much research in chemistry, biology, and material science. With this stimulating background, the efficient synthesis of not only the carbohydrate itself, but also carbohydrate-containing products, is of particular interest both in academia and in industry. In this context, glycosylation, which is a crucial organic synthetic method to attach a sugar to other sugar moieties or other molecules (aglycons), is becoming more and more important in synthetic organic chemistry and carbohydrate chemistry, and considerable attention has been directed towards the efficiency of the glycosylation method. [3] From a synthetic standpoint, the efficiency of the glycosylation reaction generally is evaluated by a high chemical yield, regioselectivity, and a/b-stereoselectivity. Unfortunately, little attention has been focused on the important issue of diastereoselectivity of the reaction between the aglycon and glycon units in glycosylation. Herein we report a novel chemical glycosylation method that alters the chiral recognition ability of the aglycon. To the best of our knowledge, this is the first demonstrated example of a chemical glycosylation with recognition of alcohol chirality.Previously, we demonstrated an enzymatic glycosylation of o-nitrophenyl b-d-galactoside and racemic secondary alcohols using b galactosidase from E. coli. [4] In this study, complete b stereoselectivity and moderate diastereoselectivity were observed. Furthermore, biocatalytic glycosylation resolution of racemic tetrahydroberberrubine was reported by Yu et al. [5] While our continuing efforts regarding this issue were unsuccessful, Fairbanks et al. recently reported a/bstereoselective glycosylation of a galactosyl trichloroacetimidate and chiral alcohols using a chiral Brønsted acid. [6,7] In that study, high b stereoselectivity, induced by a chiral Brønsted acid, was demonstrated. In this context, we expected that use of a chiral Brønsted acid in glycosylation would realize a/b stereoselective and diastereoselective chemical glycosylation by tuning the reaction conditions.To investigate our hypothesis, we selected the glucosyl trichloroacetimidate 1 a [8] and the binol-derived Brønsted acid 2 (Akiyama-Terada catalyst) [9] as glycosyl donor and chiral Brønsted acids, ...

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“…clearly affect the isomeric ratios obtained. 67 Similarly, the β-glycosylation of compound 8a at 32 °C with acetone as a cosolvent was found to furnish a more or less equimolar mixture of isomers, whereas a higher selectivity was observed upon incubation at 40 °C in combination with DMSO ( dr = 44/56 and 71/29, respectively). A more detailed study on the influence of reaction conditions on the enantioselectivity of transferase-catalyzed transformations has not been published yet and could thus constitute a suitable topic for prospective research.…”

Section: Resultsmentioning

confidence: 96%

Chemoenzymatic Approach toward the Synthesis of 3-O-(α/β)-Glucosylated 3-Hydroxy-β-lactams

et al. 2018

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Glycosylation significantly alters the biological and physicochemical properties of small molecules. β-Lactam alcohols comprise eligible substrates for such a transformation based on their distinct relevance in the chemical and medicinal community. In this framework, the unprecedented enzymatic glycosylation of the rigid and highly strained four-membered β-lactam azaheterocycle was studied. For this purpose, cis-3-hydroxy-β-lactams were efficiently prepared in three steps by means of a classical organic synthesis approach, while a biocatalytic step was implemented for the selective formation of the corresponding 3-O-α- and -β-glucosides, hence overcoming the complexities typically encountered in synthetic glycochemistry and contributing to the increasing demand for sustainable processes in the framework of green chemistry. Two carbohydrate-active enzymes were selected based on their broad acceptor specificity and subsequently applied for the α- or β-selective formation of β-lactam-sugar adducts, using sucrose as a glucosyl donor.

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Unique biocatalytic resolution of racemic tetrahydroberberrubine via kinetic glycosylation and enantio-selective sulfation

Cited by 16 publications

References 18 publications

Chiral Brønsted Acid Mediated Glycosylation with Recognition of Alcohol Chirality

Chiral Brønsted Acid Mediated Glycosylation with Recognition of Alcohol Chirality

Chiral Brønsted Acid Mediated Glycosylation with Recognition of Alcohol Chirality

Chemoenzymatic Approach toward the Synthesis of 3-O-(α/β)-Glucosylated 3-Hydroxy-β-lactams

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