One-Pot Stereoselective Synthesis of C-Glycosyl Amino Acids with Vicinal Stereocenters

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

A palladium-catalyzed cascade coupling between glycals and racemic α-nitroesters enables the stereoselective construction of C-glycosyl amino acids bearing two contiguous stereocenters, achieving dual stereocontrol (exclusive β-C1, up to 10:1 diastereomeric ratio at C7). This one-pot protocol room temperature accommodates diverse substrates (25 examples). Mechanistic studies demonstrate that decarboxylation-induced C4-oxyanion directs 1,4-syn selectivity, while steric modulation governs C7 stereochemistry. Synthetic versatility is evidenced by gram-scale synthesis late-stage functionalization trihydroxy C-glycosides, 2,3-dideoxy sugars, 4-O-amino acid conjugates.

Язык: Английский

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Palladium-Catalyzed O-Glycosylation through π–π Interactions

Organic Letters, Год журнала: 2024, Номер 26(25), С. 5396 - 5401

Опубликована: Июнь 13, 2024

A stereodivergent synthesis of β- and α-O-glycosides using 3-O-quinaldoyl glucals was developed by palladium catalysis at 60 110 °C respectively. Various alcohols, monosaccharides, amino acid were glycosylated to form α- products in good yields with high stereoselectivity. Mechanistic studies indicated no classic Pd–N (quinoline) coordination, but π–π stacking interactions promoted the anomeric stereodiversity. The practicality demonstrated glycosylating natural products/drugs synthesizing a complex tetrasaccharide.

Язык: Английский

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Stereoselective synthesis of C-glycosides from glycals and organotrifluoroborate salts

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Harnessing aryltrifluoroborates' stability and reactivity, we developed a Pd-catalyzed stereoselective C-glycosylation under ambient conditions, yielding diverse C-aryl glycosides with exclusive α-stereoselectivity compatibility hydroxyl, amide, amine groups. This method enables functionalization to produce unprotected C-pyranosides, 2,3-dideoxy 2,3-epoxy sugars, late-stage of natural products drugs.

Язык: Английский

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Cobalt-Catalyzed versus Base-Promoted Skeletal- and Stereodivergent Synthesis of Bicyclic α-C-, β-O-, and α-O-Glycosides

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 9, 2025

A stereodivergent synthesis of bicyclic α-C-, β-O-, and α-O-glycosides is achieved with nonprecious Co(dpm)3, K2CO3, DBU, respectively. Cobalt-catalyzed decarboxylative allylation 2,3-unsaturated 4-keto glycosyl carbonates 1,3-diketones delivers α-C-glycosides in good yields exclusive chemo- regiocontrol excellent diastereoselectivity (>20:1 dr). K2CO3 enables β-O-glycosides via a cascaded intermolecular Michael addition/SN2-like cyclization, whereas DBU promotes further C5 epimerization to give α-O-glycosides. Mechanistic studies (deuterium labeling intermediate capturing) validate the pathways. Gram-scale late-stage functionalization pharmaceuticals demonstrate practicality.

Язык: Английский

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Highly Regio-/Stereoselective Synthesis of Carbohydrates with Unsaturated Glycosyl Donors under Mild Conditions

Synlett, Год журнала: 2024, Номер unknown

Опубликована: Июнь 19, 2024

Abstract Carbohydrates and their conjugates play important roles in life activities drug development. Our group was committed to the general effective glycosylation methods application chemical biology using unsaturated glycosyl donors. In past five years, we have reported several synthetic strategies with high stereoselectivity milder conditions compared previous works. particular, chemo-/regio- stereoselective O-glycosylation, C-glycosylation S-glycosylation could be achieved via palladium catalysis under open-air at room temperature. this Account, will introduce our research progress constructing four types of glycosides. 1 Introduction 2 Stereoselective Synthesis O-Glycosides 3 C-Glycosides 4 N-Glycosides 5 S-Glycosides 6 Conclusion

Язык: Английский

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Aldehyde‐Mediated Open‐Air Stereoselective β‐Glycosylation of Glycals: An Expeditious Route towards Glycosyl‐Ester Synthesis

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(21), С. 4478 - 4484

Опубликована: Июль 26, 2024

Abstract The study introduces a method for achieving selective synthesis of β‐glycosyl esters through the reaction glycals with carboxylic acids. This process is characterized by stereoselectivity, operating under mild conditions and in an open‐air environment mediated aldehyde. Detailed investigations control experiments indicate significance benzaldehyde conjunction atmospheric air facilitating this transformation. method's versatility evident its broad substrate scope, accommodating various acid derivatives electron‐releasing electron‐neutral functional groups. practical applicability protocol demonstrated successfully esterifying different drugs, including indomethacin, tolmetin, stearic acid, resulting production novel compounds excellent yields. Mechanistic studies, supported controlled experiments, highlight formation glycal epoxide as intermediate reactions.

Язык: Английский

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Stereoselective synthesis of 3-sulfone sugars via cobalt catalysis

Journal of Carbohydrate Chemistry, Год журнала: 2024, Номер 43(3), С. 70 - 89

Опубликована: Март 23, 2024

Язык: Английский

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