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

Stereoselective P(III)‐Glycosylation for the Preparation of Phosphinated Sugars DOI Open Access

Xuan Zhang,

Xian‐Xiao Chen,

Zihan Li

и другие.

Angewandte Chemie, 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

Reaction Optimization of Strontium Perchlorate Catalyzed Novel Protocol for Stereoselective Synthesis of Dihydropyrimidinones DOI

Divya Chauhan,

Harish Kumar Chopra, Surendra Kumar Nayak

и другие.

Current Organic Synthesis, Год журнала: 2023, Номер 21(1), С. 78 - 90

Опубликована: Апрель 18, 2023

Hydrated strontium perchlorate [Sr(ClO4)2.3H2O] acts as a very strong oxidizing and dehydrating agent. Until now, it could not be reported catalyst in dehydration mechanism-based organic synthetic reactions. Therefore, is important to find whether an effective for one-pot multicomponent reactions (MCRs).The main objective of the present work development novel process synthesis 1,4-dihydropyrimidinones through strategy using hydrated Sr(ClO4)2 catalyst. Furthermore, includes optimization, stereoselectivity, spectroscopic characterization synthesized compounds.Conventional microwave-supported 20 mol % via solvent-free reaction was discovered new catalytic MCR methodology. The box-Behnken design approach advanced analytical techniques were used optimization analysis.The results confirmed that Sr(ClO4)2; works efficient under both conventional microwave heating. It laboratory stereoselectively with moderate excellent yield without any undesirable effect. Microwave heating provided desired product within 1-4 minutes. Moreover, this method provides easy isolation pure products simply by recrystallization, use chromatographic purification method.The simplicity neutrality conditions, post-reaction workup, higher satisfactory yield, effectiveness, diversity substrates, etc. render catalyst-based protocol stereoselective highly method. has been found safe un-der conditions no issues have faced during process.

Язык: Английский

Процитировано

0

Promoter‐Controlled Synthesis and Conformational Analysis of Cyclic Mannosides up to a 32‐mer DOI
Xiaona Li, Cristina Di Carluccio, Miao He

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(43)

Опубликована: Июль 12, 2023

Abstract Cyclodextrins are widely used as carriers of small molecules for drug delivery owing to their remarkable host properties and excellent biocompatibility. However, cyclic oligosaccharides with different sizes shapes limited. Cycloglycosylation ultra‐large bifunctional saccharide precursors is challenging due the constrained conformational spaces. Herein we report a promoter‐controlled cycloglycosylation approach synthesis α‐(1→6)‐linked mannosides up 32‐mer. thioglycosides ( Z )‐ynenoates was found be highly dependent on promoters. In particular, sufficient amount gold(I) complex played key role in proper preorganization transition state, providing 32‐mer polymannoside, which represents largest synthetic polysaccharide date. NMR experiments computational study revealed that 2‐mer, 4‐mer, 8‐mer, 16‐mer, adopted states shapes.

Язык: Английский

Процитировано

0

General strategy for the synthesis of N-glycosides DOI

Ariza Khanam,

Pintu Kumar Mandal

Elsevier eBooks, Год журнала: 2023, Номер unknown, С. 139 - 186

Опубликована: Окт. 27, 2023

Язык: Английский

Процитировано

0

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

Процитировано

0