Electrochemical Glycosylation via Halogen-Atom-Transfer for C-Glycoside Assembly DOI Creative Commons
Jun Wu, Purushothaman Rajeshwaran,

Felix Kallert

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11532 - 11544

Published: July 19, 2024

Glycosyl donor activation emerged as an enabling technology for anomeric functionalization, but aimed primarily at O-glycosylation. In contrast, we herein disclose mechanistically distinct electrochemical glycosyl bromide activations via halogen-atom transfer and C-glycosylation. The radical addition to alkenes led C-alkyl glycoside synthesis under precious metal-free reaction conditions from readily available bromides. robustness of our e-XAT strategy was further mirrored by C-aryl C-acyl glycosides assembly through nickela-electrocatalysis. Our approach provides orthogonal with expedient scope, hence representing a general method direct C-glycosides assembly.

Language: Английский

Visible light activation enables desulfonylative cross-coupling of glycosyl sulfones DOI

Quanquan Wang,

Boon Chong Lee,

Ting Jun Tan

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(12), P. 967 - 974

Published: Sept. 22, 2022

Language: Английский

Citations

78
Diversification of Glycosyl Compounds via Glycosyl Radicals DOI Creative Commons
Yi Jiang, Yijun Zhang,

Boon Chong Lee

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: June 7, 2023

Glycosyl radical functionalization is one of the central topics in synthetic carbohydrate chemistry. Recent advances metal-catalyzed cross-coupling chemistry and metallaphotoredox catalysis provided powerful platforms for glycosyl diversification. In particular, discovery new precursors conjunction with these advanced reaction technologies have significantly expanded space compound synthesis. this Review, we highlight most recent progress area starting from 2021, reports included will be categorized based on different types better clarity.

Language: Английский

Citations

67
Direct radical functionalization of native sugars DOI Creative Commons
Yi Jiang, Yi Wei, Qianyi Zhou

et al.

Nature, Journal Year: 2024, Volume and Issue: 631(8020), P. 319 - 327

Published: June 19, 2024

Abstract Naturally occurring (native) sugars and carbohydrates contain numerous hydroxyl groups of similar reactivity 1,2 . Chemists, therefore, rely typically on laborious, multi-step protecting-group strategies 3 to convert these renewable feedstocks into reagents (glycosyl donors) make glycans. The direct transformation native complex saccharides remains a notable challenge. Here we describe photoinduced approach achieve site- stereoselective chemical glycosylation from widely available sugar building blocks, which through homolytic (one-electron) chemistry bypasses unnecessary group masking manipulation. This process is reminiscent nature in its regiocontrolled generation transient glycosyl donor, followed by radical-based cross-coupling with electrophiles activation light. Through selective anomeric functionalization mono- oligosaccharides, this protecting-group-free ‘cap glycosylate’ offers straightforward access wide array metabolically robust compounds. Owing biocompatibility, the method was extended post-translational proteins.

Language: Английский

Citations

38
Direct Formation of Amide-Linked C-Glycosyl Amino Acids and Peptides via Photoredox/Nickel Dual Catalysis DOI
Xiang-Yu Ye, Guanjie Wang, Zhichao Jin

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5502 - 5510

Published: Feb. 15, 2024

Glycoproteins account for numerous biological processes including those associated with diseases and infections. The advancement of glycopeptides has emerged as a promising strategy unraveling pathways discovering novel medicines. In this arena, key challenge arises from the absence efficient synthetic strategies to access glycoproteins. Here, we present highly concise approach bridging saccharides amino acids peptides through an amide linkage. Our amide-linked C-glycosyl are synthesized cooperative Ni-catalyzed photoredox processes. catalytic process generates glycosyl radical carbonyl radical, which subsequently combine yield products. saccharide reaction partners encompass mono-, di-, trisaccharides. All 20 natural acids, peptides, their derivatives can efficiently undergo glycosylations yields ranging acceptable high, demonstrating excellent stereoselectivities. As substantial expansion applications, have shown that simple function versatile building units constructing C-glycopeptides intricate spatial complexities.

Language: Английский

Citations

26
N-glycoside synthesis through combined copper- and photoredox-catalysed N-glycosylation of N-nucleophiles DOI
Qikai Sun,

Quanquan Wang,

Wenzhuo Qin

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(5), P. 623 - 632

Published: March 1, 2024

Language: Английский

Citations

25
Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis DOI Creative Commons
Lauren E. Ehehalt, Omar M. Beleh, Isabella C. Priest

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Language: Английский

Citations

20
Titanium radical redox catalysis: Recent innovations in catalysts, reactions, and modes of activation DOI Creative Commons
Xiangyu Wu,

Yejin Chang,

Song Lin

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(7), P. 1805 - 1821

Published: July 1, 2022

Radical chemistry has emerged as a cornerstone in modern organic synthesis, providing chemists with numerous new tools to rapidly expand reactivity and chemical space academic industrial research. In this regard, titanium complexes have been recognized an attractive class of catalysts owing their rich redox activities addition the abundance low toxicity early transition metal. Traditionally employed for activation epoxides carbonyl compounds, Ti radical catalysis broken into grounds recent years, giving rise diverse repertoire useful transformations. Perspective, we highlight developments area

Language: Английский

Citations

50
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
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
Recent Advances in First-Row Transition Metal-Catalyzed Reductive Coupling Reactions for π-Bond Functionalization and C-Glycosylation DOI
Yi Wei,

Leroy Qi Hao Lin,

Boon Chong Lee

et al.

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(22), P. 3292 - 3312

Published: Nov. 2, 2023

ConspectusEfficient construction of ubiquitous carbon-carbon bonds between two electrophiles has garnered interest in recent decades, particularly if it is mediated by nonprecious, first-row transition metals. Reductive coupling advantages over traditional cross-coupling obviating the need for stoichiometric air- and moisture-sensitive organometallic reagents. By harnessing metal-catalyzed reductive as a powerful tool, intricate molecular architectures can be readily assembled through installation C-C across π systems (alkenes/alkynes) via reaction with appropriate electrophiles. Despite advances alkene difunctionalization, there remains significant potential discovery novel pathways. In this regard, development protocols that enable union challenging alkyl/alkynyl high regio- chemoselectivity highly sought-after goal.Apart from π-bond functionalization, found application carbohydrate chemistry, synthesis valuable C-glycosyl compounds. vein, suitable glycosyl donors used to generate reactive radical intermediates under conditions. Through elaborately designed reactions, these trapped furnish pharmaceutically relevant glycoconjugates. Consequently, diversification compound using metal catalysis holds strong appeal.In Account, we summarize our efforts reactions applications alkene/alkyne functionalization C-glycosylation. We will first discuss nickel (Ni)-catalyzed difunctionalization alkenes, aided an 8-aminoquinoline (AQ) directing auxiliary. Next, highlight Ni-catalyzed hydroalkylation alkenyl amides tethered similar AQ-derived Lastly, efficient 1,3-enynes involving site- stereoselective terminal alkynes alkynyl halides NHPI esters.Beyond dicarbofunctionalization, extended paradigm toward C-glycosidic linkages carbohydrates. employing earth-abundant iron (Fe)-based catalyst, show useful radicals generated chlorides These captured bond formation C-aryl, C-alkenyl, C-alkynyl compounds diastereoselectivity. Our multicomponent chlorides, aryl/alkyl iodides, isobutyl chloroformate conditions led C-acyl glycosides. addition Fe Ni, discovered Ti-catalyzed/Mn-promoted synthetic route access C-alkyl C-alkenyl compounds, electron-deficient alkenes/alkynes. further developed electron donor-acceptor (EDA) photoactivation system leveraging decarboxylative deaminative strategies C-glycosylation Ni catalysis. This approach been demonstrated selectively activate carboxyl amino motifs glycopeptide conjugates. Finally, distinct catalytic transformations bench-stable heteroaryl sulfones, achieved stereodivergent both α- β-anomers C-aryl glycosides, one which involves aryl iodides.The findings presented Account are anticipated have far-reaching implications beyond research. foresee results pave way new founded on concept coupling, leading future.

Language: Английский

Citations

32