Pd-Catalyzed Stereospecific Glycosyl Cross-Coupling of Reversed Anomeric Stannanes for Modular Synthesis of Nonclassical C-Glycosides DOI Creative Commons
Cheng Guo-qiang, Bo Yang, Zhi Yang

et al.

Precision Chemistry, Journal Year: 2024, Volume and Issue: 2(11), P. 587 - 599

Published: July 21, 2024

Nonclassical C-glycosides, distinguished by their unique glycosidic bond connection mode, represent a promising avenue for the development of carbohydrate-based drugs. However, accessibility nonclassical C-glycosides hinders broader investigations into structural features and modes action. Herein, we present first example Pd-catalyzed stereospecific glycosylation anomeric stannanes with aryl or vinyl halides. This method furnishes desired in good to excellent yields, while allowing exclusive control configuration. Of significant note is demonstration generality practicality this C-glycosylation approach across more than 50 examples, encompassing various protected unprotected saccharides, deoxy sugars, oligopeptides, complex molecules. Furthermore, biological evaluation indicates that modifications drug molecules can positively impact activity. Additionally, extensive computational studies are conducted elucidate rationale behind differences reaction reactivity, unveiling transmetalation transition state containing silver (Ag) within six-membered ring. Given its remarkable controllability, predictability, consistently high chemical selectivity stereospecificity regarding carbon Z/E configuration, outlined study offers solution longstanding challenge accessing stereocontrol.

Language: Английский

Single Electron Transfer-Induced Redox Processes Involving N-(Acyloxy)phthalimides DOI

Sushanta Kumar Parida,

Tanumoy Mandal,

Sanju Das

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(3), P. 1640 - 1683

Published: Jan. 20, 2021

The past decade has witnessed the emergence of N-(acyloxy)phthalimides (NHPI esters) and its derivatives at forefront synthetic methods facilitating construction diverse molecular frameworks from readily available carboxylic acid feedstock. NHPI esters are predisposed to undergo reductive fragmentation via a single electron transfer (SET) process under thermal, photochemical, or electrochemical conditions generate corresponding carbon- nitrogen-centered radicals that participate in multitude transformations forge carbon–carbon carbon–heteroatom bonds. chemistry involving received broad applicability not only well-designed cascade annulations but also medicinal natural product synthesis. This comprehensive Review, broadly categorized according nature bond formation, details progress made this field since initial discovery by providing representative examples with mechanistic details, an emphasis on challenges future directions.

Language: Английский

Citations

274
Recent development in the synthesis of C-glycosides involving glycosyl radicals DOI

Lin-Yi Xu,

Nai-Li Fan,

Xiang‐Guo Hu

et al.

Organic & Biomolecular Chemistry, Journal Year: 2020, Volume and Issue: 18(27), P. 5095 - 5109

Published: Jan. 1, 2020

C-Glycosylation involving glycosyl radical intermediates is a particularly effective approach to access C-glycosides, which are core units of great number natural products, bioactive compounds and marketed drugs. In this review, we summarize the progress radical-based C-glycoside synthesis between 1999-2020, focusing on stereoselectivity recently developed methodologies such as α-alkoxyacyl telluride-related, photo-mediated transition-metal catalysed reactions. Metal-mediated reductive cross coupling also covered due its close relationship with latter approaches. To introduce several strategies for achieving uncommon β-stereoselective C-glycosylation, briefly described organotin-based methods.

Language: Английский

Citations

149
Transformations of carbohydrate derivatives enabled by photocatalysis and visible light photochemistry DOI Creative Commons

Daniel J. Gorelik,

Shrey P. Desai,

Sofia Jdanova

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(4), P. 1204 - 1236

Published: Jan. 1, 2024

This review article highlights the diverse ways in which recent developments areas of photocatalysis and visible light photochemistry are impacting synthetic carbohydrate chemistry.

Language: Английский

Citations

30
Utilization of C(sp3)‐Carboxylic Acids and Their Redox‐Active Esters in Decarboxylative Carbon−Carbon Bond Formation DOI
Sukhen Karmakar,

Arundutt Silamkoti,

Nicholas A. Meanwell

et al.

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(15), P. 3693 - 3736

Published: May 11, 2021

Abstract Over the last several years, radical‐mediated decarboxylative cross‐coupling reactions employing alkyl carboxylic acids have emerged as a powerful tool for regiospecific construction of carbon−carbon bonds. Under thermal or photocatalytic conditions, wide variety C( sp 3 )‐carboxylic and their redox‐active esters undergo C−C bond formation with suitable reactant partners, leading to complex chemical scaffolds wide‐ranging applications. This synthetic strategy has advantages over more conventional organometallic reagents, including abundant starting material availability high functional group tolerance associated mild reaction conditions. review article highlights recent developments in functionalization α‐heteroatom‐substituted well challenging unactivated acids, representative examples discussed against backdrop insightful comments on mechanisms. In addition, synthesis natural products, drug molecules, late‐stage modification bioactive molecules this non‐traditional are included. been categorized into three main sections that organized around type being forged: )−C( 2 ), ). Further, separately each section. magnified image

Language: Английский

Citations

90
Generation of Glycosyl Radicals from Glycosyl Sulfoxides and Its Use in the Synthesis ofC‐linked Glycoconjugates DOI
Weidong Shang,

Shengnan Su,

Rong Shi

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(1), P. 385 - 390

Published: Sept. 21, 2020

We here report glycosyl sulfoxides appended with an aryl iodide moiety as readily available, air and moisture stable precursors to radicals. These could be converted radicals by way of a rapid efficient intramolecular radical substitution event. The use this type enabled the synthesis various complex C-linked glycoconjugates under mild conditions. This reaction performed in aqueous media is amenable glycopeptidomimetics carbohydrate-DNA conjugates.

Language: Английский

Citations

89
Visible‐Light‐Promoted Stereoselective C(sp3)−H Glycosylation for the Synthesis of C‐Glycoamino Acids and C‐Glycopeptides DOI

Rupeng Qi,

Chao Wang,

Zijian Ma

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(24)

Published: March 22, 2022

The glycosylative modification of peptides could improve the pharmacological properties peptide drugs and deliver them efficiently to target sites. Compared with O-/N-glycosides, C-glycosides exhibit more metabolic stability. We here disclose first example visible-light-promoted Cu-catalyzed stereoselective C-glycosylation. mild reaction conditions are compatible various carbohydrate substrates, as demonstrated a series monosaccharides disaccharide, amenable synthesis wide variety C-glycoamino acids C-glycopeptidomimetics good yields excellent stereoselectivities. dual-functional photocatalyst formed in situ via coordination glycine derivative chiral phosphine Cu complex not only catalyze photoredox process but also control stereoselectivity glycosylation reaction.

Language: Английский

Citations

62
Synthesis of C-glycosides by Ti-catalyzed stereoselective glycosyl radical functionalization DOI Creative Commons
Yi Jiang, Quanquan Wang, Xinglong Zhang

et al.

Chem, Journal Year: 2021, Volume and Issue: 7(12), P. 3377 - 3392

Published: Oct. 13, 2021

Language: Английский

Citations

59
Exploiting photoredox catalysis for carbohydrate modification through C–H and C–C bond activation DOI
Andrey Shatskiy, Elena V. Stepanova, Markus D. Kärkäs

et al.

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(11), P. 782 - 805

Published: Sept. 21, 2022

Language: Английский

Citations

49
Recent development of stereoselective C-glycosylation via generation of glycosyl radical DOI Creative Commons
Titli Ghosh, Toshiki Nokami

Carbohydrate Research, Journal Year: 2022, Volume and Issue: 522, P. 108677 - 108677

Published: Sept. 17, 2022

Language: Английский

Citations

42
Generation and Use of Glycosyl Radicals under Acidic Conditions: Glycosyl Sulfinates as Precursors DOI

Shiyang Xu,

Wei Zhang,

Caiyi Li

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(16)

Published: Feb. 10, 2023

We herein report a method that enables the generation of glycosyl radicals under highly acidic conditions. Key to success is design and use sulfinates as radical precursors, which are bench-stable solids can be readily prepared from commercial starting materials. This development allows installation units onto pyridine rings directly by Minisci reaction. further demonstrate utility this in late-stage modification complex drug molecules, including anticancer agent camptothecin. Experimental studies provide insight into reaction mechanism.

Language: Английский

Citations

35