Radical N-Glycosylation of Heterocycles with 1-Hydroxycarbohydrates Enabled by Copper Metallaphotoredox Catalysis DOI Creative Commons
Xiang‐Guo Hu, Dapeng Liu,

Zhang Shao-sen

и другие.

Research Square (Research Square), Год журнала: 2023, Номер unknown

Опубликована: Дек. 13, 2023

Abstract N-Glycosylated heterocycles play important roles in biological systems and drug development. The synthesis of these compounds heavily relies on ionic N-glycosylation, which is usually constrained by factors like labile glycosyl donors, precious metal catalysts, stringent conditions. Herein, we report an unprecedented radical-based method for synthesizing N -glycosides leveraging copper metallaphotoredox catalysis. Complementing with the well-established approaches, our employs inexpensive photo- copper- catalysts can tolerate some extent water. Furthermore, readily available stable 1-hydroxycarbohydrates are successfully utilized first time N-glycosylation. reaction exhibits a broad substrate scope, encompassing 76 examples, demonstrates high stereoselectivity, favoring 1,2-trans selectivity furanoses α-selectivity pyranoses. It also site-selectivity substrates containing multiple N-atoms. synthetic utility was showcased through late-stage functionalization bioactive pharmaceuticals Olaparib, Axitinib, Metaxalone. Mechanistic studies proved presence intermediates importance

Язык: Английский

Nucleoside chemistry: a challenge best tackled together DOI Creative Commons
Sarah Westarp, Peter Neubauer, Anke Kurreck

и другие.

Comptes Rendus Chimie, Год журнала: 2025, Номер 28(G1), С. 319 - 326

Опубликована: Март 21, 2025

Язык: Английский

Процитировано

0
Mild Approach to Nucleoside Analogues via Photoredox/Cu-Catalyzed Decarboxylative C–N Bond Formation. Total Synthesis of Oxetanocin A DOI
Ruonan Wang, Hao Xu, Arpan Banerjee

и другие.

Organic Letters, Год журнала: 2023, Номер 26(14), С. 2691 - 2696

Опубликована: Ноя. 27, 2023

The conventional N-glycosylation methods for nucleoside synthesis usually require strongly acidic or basic conditions. Here we report the decarboxylative C(sp3)–N coupling of glycosyl N-hydroxyphthalimide esters with nucleobases via dual photoredox/Cu catalysis, which offered a mild approach to analogues. A total oxetanocin A, an antiviral natural product containing oxetanose moiety, has been achieved by using this method.

Язык: Английский

Процитировано

6
Additive-assisted synthesis of α-Kdo glycosides with peracetylated glycosyl ynenoate as a donor DOI
Miao He,

Siqian Lu,

Hongyu Chen

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(12), С. 2365 - 2369

Опубликована: Янв. 1, 2024

Additive-assisted α-selective Kdo glycosylation using a peracetylated ynenoate is described for stereoselective synthesis of the protected trisaccharide variant relevant to lipopolysaccharide Coxiella burnetii strain Nine Mile.

Язык: Английский

Процитировано

2
Microwave-assisted synthesis of highly sulfated mannuronate glycans as potential inhibitors against SARS-CoV-2 DOI

Yirong Zhu,

Xiaotong Wang,

Siqian Lu

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(19), С. 3986 - 3994

Опубликована: Янв. 1, 2024

Sulfated mannuronate glycans with up to 17 sulfation sites were synthesized using a microwave-assisted approach and evaluated as inhibitors against SARS-CoV-2.

Язык: Английский

Процитировано

2
A Radical Activation Strategy for Versatile and Stereoselective N‐Glycosylation DOI

Wenyan Ding,

Xinyu Chen,

Zuyao Sun

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(36)

Опубликована: Июнь 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

Язык: Английский

Процитировано

2
Photolabile ortho‐Nitro‐Benzyl Carbonate as a Permanent Hydroxyl Protecting Group for the Synthesis of Digalactosyl Diacylglycerol DOI
Jibin Zheng, Hongyu Chen,

Jintao Shang

и другие.

Chinese Journal of Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Окт. 16, 2024

Comprehensive Summary Traditional protecting groups are often removed under harsh conditions with potentially hazardous reagents, thereby impeding the convenient synthesis of oligosaccharides and glycosides. Herein, we present to utilize photolabile ortho ‐nitro‐benzyl carbonate ( o NBC) as a permanent hydroxyl group for stereocontrolled The Ph 3 PO‐modulated glycosylation strongly disarmed per‐ O ‐ NBC‐protected glycosyl ynenoates preferred afford glycosides excellent α‐selectivities via β‐phosphonium transition state. Based on NBC‐mediated galactosylation, glycolipid digalactosyl diacylglycerol (DGDG) containing six double bonds two esters was achieved in straightforward manner.

Язык: Английский

Процитировано

2
A Radical Activation Strategy for Versatile and Stereoselective N‐Glycosylation DOI

Wenyan Ding,

Xinyu Chen,

Zuyao Sun

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(36)

Опубликована: Июнь 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.

Язык: Английский

Процитировано

1
Stereoselective P(III)‐Glycosylation for the Preparation of Phosphinated Sugars DOI
Xuan Zhang,

Xian‐Xiao Chen,

Zi‐Han Li

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Дек. 6, 2024

Abstract Most of the reported work focus on development O ‐, N C ‐ and S ‐glycosylation methods. However, no study explores P(III)‐glycosylation reaction. Herein we describe a convenient protocol to realize process. A simple β ‐phosphino ester is adopted as P(III)‐transfer reagent for this new type glycosylation via nucleophilic substitution release strategy. Diverse phosphine units are introduced anomeric center various sugars efficiently with excellent stereoselectivity. The value method showcased by prepared P(III)‐sugars novel linkers in bioactive molecule conjugation, chiral ligands metal‐catalyzed asymmetric allylic substitutions organocatalysts. Preliminary mechanistic studies corroborated designed

Язык: Английский

Процитировано

0
Synthesis of Natural and Sugar-Modified Nucleosides Using the Iodine/Triethylsilane System as N-Glycosidation Promoter DOI Open Access
Martina Cimafonte, Anna Esposito, Maria De Fenza

и другие.

International Journal of Molecular Sciences, Год журнала: 2024, Номер 25(16), С. 9030 - 9030

Опубликована: Авг. 20, 2024

The reagent system based on the combined use of Et3SiH/I2 acts as an efficient N-glycosidation promoter for synthesis natural and sugar-modified nucleosides. An analysis reaction stereoselectivity in absence C2-positioned stereodirecting groups revealed high selectivity with six-membered substrates, depending nucleophilic character nucleobase or anomerization reactions. synthetic utility Et3SiH/I2-mediated was highlighted by its investigational drug apricitabine.

Язык: Английский

Процитировано

0
Ph3PO-Modulated Kdo Glycosidation for Stereoselective Synthesis of β-Kdo-Containing Disaccharides DOI
Miao He,

Ruihao Yu,

Jibin Zheng

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 30, 2024

A Ph3PO-modulated β-selective Kdo glycosidation approach is developed for the stereoselective synthesis of β-Kdo glycosides. With readily available per-O-acetylated ynenoate as donor, glycosylation with a series alcohols in presence Ph3PAuOTf and Ph3PO toluene at low temperatures afforded desired glycosides good to excellent β-selectivities. Furthermore, was effectively applied β-(2→4)- β-(2→8)-linked Kdo-Kdo disaccharides further biological studies.

Язык: Английский

Процитировано

0