Palladium-Catalyzed Regio- and Stereoselective Glycosylation of Azole Heterocycles Enables Access to Diverse Heterocyclic N-Glycosides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(32), P. 6878 - 6883

Published: Aug. 6, 2024

An efficient and practical glycosylation platform for synthesizing

Language: Английский

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Palladium-Catalyzed Stereospecific Glycosylation Enables Divergent Synthesis of N–O-Linked Glycosides

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

We present a versatile palladium-catalyzed glycosylation platform that enables facile access to structurally diverse N-O-linked glycosides with constantly excellent regio- and stereoselectivities. Importantly, this approach offers broad substrate scope, low catalyst loadings, outstanding chemoselectivity, allowing for the selective reaction of oximes/hydroximic acids over hydroxyl groups would otherwise pose challenges in conventional methods. The synthetic utility method is further exemplified through range transformations late-stage modification bioactive molecules. Overall, our provides an efficient toolkit synthesis glycosides, which will facilitate their subsequent biological evaluations.

Language: Английский

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A Radical Activation Strategy for Versatile and Stereoselective N‐Glycosylation

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 5, 2024

Previous N-glycosylation approaches have predominately involved acidic conditions, facing challenges of low stereoselectivity and limited scope. Herein, we introduce a radical activation strategy that enables versatile stereoselective using readily accessible glycosyl sulfinate donors under basic conditions exhibits exceptional tolerance towards various N-aglycones containing alkyl, aryl, heteroaryl nucleobase functionalities. Preliminary mechanistic studies indicate pivotal role iodide, which orchestrates the formation from subsequent generation key intermediate, configurationally well-defined is subsequently attacked by an N-aglycone in stereospecific S

Language: Английский

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A Radical Activation Strategy for Versatile and Stereoselective N‐Glycosylation

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(36)

Published: June 5, 2024

Abstract Previous N‐glycosylation approaches have predominately involved acidic conditions, facing challenges of low stereoselectivity and limited scope. Herein, we introduce a radical activation strategy that enables versatile stereoselective using readily accessible glycosyl sulfinate donors under basic conditions exhibits exceptional tolerance towards various N‐aglycones containing alkyl, aryl, heteroaryl nucleobase functionalities. Preliminary mechanistic studies indicate pivotal role iodide, which orchestrates the formation from subsequent generation key intermediate, configurationally well‐defined is subsequently attacked by an N‐aglycone in stereospecific S N 2 manner to give desired N‐glycosides. An alternative route involving coupling nitrogen‐centered also proposed, affording exclusive 1,2‐ trans product. This novel approach promises broaden synthetic landscape N‐glycosides, offering powerful tool for construction complex glycosidic structures mild conditions.

Language: Английский

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Stereoselective Synthesis of Glycosides via Tsuji–Trost Type Glycosylation Using 3,4‐Carbonate Galactals

The Chemical Record, Journal Year: 2024, Volume and Issue: 24(9)

Published: Aug. 21, 2024

Pd-catalyzed stereoselective glycosylations using unsaturated sugar derivatives, glycals, have been successfully achieved in recent years. This review focuses on approaches to control the stereoselectivities of glycosides via π-allyl intermediates that mimic Tsuji-Trost asymmetric allylic alkylation reactions, enabling stereoselectivity through rational design. In reaction process, zwitterionic Pd-π-allyl complexes, formed after oxidative addition and decarboxylation, play a crucial role increasing reactivities enhancing α- β-glycosides. We summarized recently developed type 3,4-carbonate galactals, featuring high efficiency, exclusive stereoselectivities, broad scope including O-, N-, S-, C-glycosylations.

Language: Английский

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