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

Stereoselective alkylC-glycosylation of glycosyl estersviaanomeric C–O bond homolysis: efficient access toC-glycosyl amino acids andC-glycosyl peptides DOI Creative Commons

Anrong Chen,

Shiyin Zhao,

Yang Han

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(27), P. 7569 - 7580

Published: Jan. 1, 2023

A novel photoredox-catalyzed radical conjugate addition of 1,4-dihydropyridine-derived glycosyl esters and dehydroalanine derivatives via anomeric C(sp 3 )–O bond homolysis to construct C -glycosyl amino acids peptides is for the first time described.

Language: Английский

Citations

33
Catalytic and Photochemical Strategies to Stabilized Radicals Based on Anomeric Nucleophiles DOI
Feng Zhu, Shuo‐Qing Zhang, Zhenhao Chen

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(25), P. 11102 - 11113

Published: June 1, 2020

Carbohydrates, one of the three primary macromolecules living organisms, play significant roles in various biological processes such as intercellular communication, cell recognition, and immune activity. While majority established methods for installation carbohydrates through anomeric carbon rely on nucleophilic displacement, radicals represent an attractive alternative because their functional group compatibility high selectivities. Herein, we demonstrate that nucleophiles C1 stannanes can be converted into by merging Cu(I) catalysis with blue light irradiation to achieve highly stereoselective C(sp3)-S cross-coupling reactions. Mechanistic studies DFT calculations revealed C-S bond-forming step occurs via transfer radical directly a sulfur electrophile bound Cu(II) species. This pathway complements chain observed photochemical metal-free conditions where disulfide initiator activated Lewis base additive. Both strategies utilize efficient donors switch from ionic pathway. Taken together, stability glycosyl nucleophiles, broad substrate scope, selectivities thermal protocols make this novel cross coupling practical tool late-stage glycodiversification bioactive natural products drug candidates.

Language: Английский

Citations

58
Synthesis of C-acyl furanosides via the cross-coupling of glycosyl esters with carboxylic acids DOI Creative Commons

Yongliang Wei,

Jenny K.W. Lam, Tianning Diao

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(34), P. 11414 - 11419

Published: Jan. 1, 2021

C-Acyl furanosides are versatile synthetic precursors to a variety of natural products, nucleoside analogues, and pharmaceutical molecules. This report addresses the unmet challenge in preparing C-acyl by developing cross-coupling reaction between glycosyl esters carboxylic acids. A key step is photoredox activation ester, which promotes homolysis strong anomeric C-O bond through CO2 evolution afford radicals. method embraces large scope furanoses, pyranoses, acids, readily applicable synthesis thymidine analogue diplobifuranylone B, as well late-stage modification (+)-sclareolide. The convenient preparation redox active ester from native sugars compatibility with common furanoses exemplifies potential this medicinal chemistry.

Language: Английский

Citations

55
Site-selective redox isomerizations of furanosides using a combined arylboronic acid/photoredox catalyst system DOI Creative Commons

Victoria Dimakos,

Daniel J. Gorelik,

Hsin Y. Su

et al.

Chemical Science, Journal Year: 2020, Volume and Issue: 11(6), P. 1531 - 1537

Published: Jan. 1, 2020

The combined action of boronic acid, photoredox catalyst and hydrogen atom transfer mediator enables the transformation furanosides to 2-keto-3-deoxyfuranosides, a synthetic analog process catalyzed by ribonucleotide reductase enzymes.

Language: Английский

Citations

54
An organophotoredox-catalyzed redox-neutral cascade involving N-(acyloxy)phthalimides and maleimides DOI
Sanju Das,

Sushanta Kumar Parida,

Tanumoy Mandal

et al.

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(10), P. 2256 - 2262

Published: Jan. 1, 2021

A mild and efficient organophotoredox-catalyzed redox-neutral cascade involving maleimides N-(acyloxy)phthalimides allowing the synthesis of otherwise inaccessible Z-selective alkoxy-alkylidenesuccinimides is achieved.

Language: Английский

Citations

45
Catalytic Multicomponent Synthesis ofC‐Acyl Glycosides by Consecutive Cross‐Electrophile Couplings DOI
Yi Jiang,

Kai Yang,

Yi Wei

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(46)

Published: Sept. 27, 2022

C-Acyl glycosides are versatile intermediates to natural products and medicinally relevant entities. Conventional cross-coupling strategies secure these molecules often relied on two-component manifolds in which a glycosyl precursor is coupled with an acyl donor (pre-synthesized or generated situ) under transition metal dual catalysis forge C-C bond. Here, we disclose three-component Ni-catalyzed reductive regime that facilitates the chemoselective union of halides, organoiodides commercially available isobutyl chloroformate as CO surrogate. The method tolerates multiple functionalities resulting obtained high diastereoselectivities. Theoretical calculations provide mechanistic rationale for unexpectedly chemoselectivity sequential cross-electrophile couplings. This approach enables expeditious assembly difficult-to-synthesize C-acyl glycosides, well late-stage keto-glycosylation oligopeptides.

Language: Английский

Citations

33
Recent Advances and Development in Visible‐Light‐Mediated Glycosylation: An Expanding Research Area in Glycochemistry DOI

Zanjila Azeem,

Pintu Kumar Mandal

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(17), P. 2818 - 2849

Published: July 7, 2023

Abstract In the last fifteen years, development of visible‐light photocatalysis, metal/photoredox dual catalysis has become forefront as a new paradigm in organic synthesis well carbohydrate chemistry. It led to discovery unprecedented transformations and also improvement known reactions under mild conditions, employing simple household light sources bench‐stable precursors, which meet requirements green chemistry sustainable excellent yield stereocontrol. general sense, exploitation photoredox hinges on capability photocatalyst or redox mediator transform visible into chemical energy via photo‐irradiated SET (single electron transfer), PET (photoinduced HAT (hydrogen atom XAT (halogen transfer) potentially unlock unique reaction pathways, thereby generating diverse array reactive intermediates. view type, mechanism, status, this review will systematically summarize latest advances visible‐light‐promoted photocatalytic glycosylation reactions, are driven by single photoactivity donor‐acceptor (EDA) complexes.

Language: Английский

Citations

20
Stereospecific Photoredox‐Catalyzed Vinylations to Functionalized Alkenes and C‐Glycosides** DOI Creative Commons
Kumar Bhaskar Pal, Ester Maria Di Tommaso, A. Ken Inge

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 15, 2023

We report an efficient radical-mediated C-C coupling through photoredox-catalyzed reactions of 4-alkyl-dihydropyridines (DHPs) and vinylbenziodoxol(on)es (VBX, VBO). This transition-metal-free mild photocatalytic method has excellent functional group tolerance affords vinylated products in good yields, with complete retention the alkene configuration. The utility methodology is demonstrated by diastereoselective synthesis C-vinyl glycosides. Preliminary mechanistic studies suggest that bond formation stereospecific proceeds a concerted radical transition state.

Language: Английский

Citations

19
Recent advances in glycosylation involving novel anomeric radical precursors DOI

Anrong Chen,

Lili Xu, Zhenghong Zhou

et al.

Journal of Carbohydrate Chemistry, Journal Year: 2021, Volume and Issue: 40(7-9), P. 361 - 400

Published: Nov. 22, 2021

Radical glycosylation has gradually become a powerful and effective method to synthesize carbohydrate mimetics as reactions via radical intermediates usually provide excellent functional group compatibility good anomeric selectivity. Novel glycosyl precursors have been identified donors in access C-, S- Se-glycosides. This review aims at summarizing the remarkable advances illuminate potential future research directions. Herein, most recent literature concerning is covered with specific emphasis on precursor design along discussions of consequential mechanisms.

Language: Английский

Citations

41
Glycosyl-Radical-Based Synthesis of C-Alkyl Glycosides via Photomediated Defluorinative gem-Difluoroallylation DOI

Cai-Yi Li,

Yue Ma, Zhiwei Lei

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(22), P. 8899 - 8904

Published: Nov. 2, 2021

We have developed a stereoselective, glycosyl radical-based method for the synthesis of C-alkyl glycosides via photomediated defluorinative gem-difluoroallylation reaction. demonstrate first time that radicals, generated from bromides, can readily participate in radical polar crossover process, affording diverse array gem-difluoroalkene containing C-glycosides. Notable features this include scalability, mild conditions, broad substrate scope, and suitability late-stage modification complex molecules.

Language: Английский

Citations

39