Ligand‐Controlled Stereoselective Synthesis of 2‐Deoxy‐β‐C‐glycosides by Cobalt Catalysis DOI

Bingxue Liu,

Deguang Liu, Xianle Rong

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(22)

Published: March 17, 2023

2-Deoxy-β-C-glycosides represent an important class of carbohydrates that are present in many bioactive molecules. However, owing to the lack substituents at C2 position, stereoselective synthesis 2-deoxy-β-C-glycosides is highly challenging. Herein, we report a ligand-controlled C-alkyl glycosylation reaction access 2-deoxy-β-C-alkyl glycosides from readily available glycals and alkyl halides. This method exhibits broad substrate scope excellent diastereoselectivity under very mild conditions. In addition, unprecedented stereodivergent 2-deoxy-C-ribofuranosides achieved using different chiral bisoxazoline ligands. Mechanistic studies suggest hydrometallation glycal with bisoxazoline-ligated Co-H species may be turnover-limiting stereodetermining step this transformation.

Language: Английский

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

25
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
Selective deoxygenative alkylation of alcohols via photocatalytic domino radical fragmentations DOI Creative Commons
Hongmei Guo, Xuesong Wu

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Sept. 10, 2021

Abstract The delivery of alkyl radicals through photocatalytic deoxygenation primary alcohols under mild conditions is a so far unmet challenge. In this report, we present one-pot strategy for deoxygenative Giese reaction with electron-deficient alkenes, by using xanthate salts as alcohol-activating groups radical generation visible-light photoredox in the presence triphenylphosphine. convenient and high reactivity sequential C–S/C–O bond homolytic cleavage enable efficient primary, secondary tertiary diverse functionality structure to generate corresponding radicals, including methyl radical. Moreover, chemoselective monodeoxygenation diols achieved via selective formation salts.

Language: Английский

Citations

82
In-Situ Bromination Enables Formal Cross-Electrophile Coupling of Alcohols with Aryl and Alkenyl Halides DOI
K. Benjamin, Jonas K. Widness, Michael M. Gilbert

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 12(1), P. 580 - 586

Published: Dec. 21, 2021

Although alcohols are one of the largest pools alkyl substrates, approaches to utilize them in cross-coupling and cross-electrophile coupling limited. We report use 1° 2° with aryl vinyl halides form C(sp

Language: Английский

Citations

79
Aryl Radical Activation of C–O Bonds: Copper-Catalyzed Deoxygenative Difluoromethylation of Alcohols DOI
Aijie Cai, Wenhao Yan, Wei Liu

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(26), P. 9952 - 9960

Published: June 28, 2021

Given their ubiquity in natural products and pharmaceuticals, alcohols represent one of the most attractive starting materials for construction C–C bonds. We report herein first catalytic strategy to harness reactivity aryl radicals activation C–O bonds alcohol-derived xanthate esters, allowing discovery deoxygenative difluoromethylation reaction. Under copper-catalyzed conditions, a wide variety alkyl readily synthesized from alcohol feedstocks, were activated by catalytically generated converted alkyl-difluoromethane via radical intermediates. This scalable protocol exhibits broad substrate scope functional group tolerance, enabling late-stage modification complex pharmaceutical agents. A one-pot has been developed that allows direct use free without purification esters. Mechanistic studies are consistent with hypothesis being formed initiating cleavage generate as key approach represents new cross-coupling partners.

Language: Английский

Citations

71
Stereoselective Synthesis of C‐Vinyl Glycosides via Palladium‐Catalyzed C−H Glycosylation of Alkenes DOI
Qikai Sun, Huixing Zhang,

Quanquan Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(36), P. 19620 - 19625

Published: July 6, 2021

C-vinyl glycosides are an important class of carbohydrates and pose a unique synthetic challenge. A new strategy has been developed for stereoselective synthesis via Pd-catalyzed directed C-H glycosylation alkenes with glycosyl chloride donors using easily removable bidentate auxiliary. Both the γ bond allylamines δ homoallyl amine substrates can be glycosylated in high efficiency excellent regio- stereoselectivity. The resulting further converted to variety C-alkyl stereospecificity. These reactions offer broadly applicable method streamline complex from accessible starting materials.

Language: Английский

Citations

68
Synthesis of C-Mannosylated Glycopeptides Enabled by Ni-Catalyzed Photoreductive Cross-Coupling Reactions DOI
Runyu Mao,

Shiyi Xi,

Sayali Shah

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(32), P. 12699 - 12707

Published: Aug. 4, 2021

The biological functions of tryptophan C-mannosylation are poorly understood, in part, due to a dearth methods for preparing pure glycopeptides and glycoproteins with this modification. To address issue, efficient scalable required installing protein Here, we describe unique Ni-catalyzed cross-coupling conditions that utilize photocatalysis or Hantzsch ester photoreductant couple glycosyl halides (hetero)aryl bromides, thereby enabling the α-C-mannosylation 2-bromo-tryptophan, peptides thereof, bromides more generally. We also report 2-(α-d-mannopyranosyl)-L-tryptophan undergoes facile anomerization presence acid: something must be considered when handling These developments enabled first automated solid-phase peptide syntheses C-mannosylated glycopeptides, which used map epitope an antibody, as well providing verified synthesis Carmo-HrTH-I, insect hormone. complement approach, performed late-stage on diverse array peptides, demonstrating broad scope utility methodology glycopeptides.

Language: Английский

Citations

66
Photoredox-Catalyzed Stereoselective Synthesis of C-Nucleoside Analogues from Glycosyl Bromides and Heteroarenes DOI
Liwen Xia, Wenjing Fan, Xiang‐Ai Yuan

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(15), P. 9397 - 9406

Published: July 14, 2021

C-nucleosides, analogues of nucleosides by replacing a C–N glycosidic bond with C–C bond, are potential anticancer or antiviral agents. Synthesis C-nucleoside enabled photoredox-catalyzed radical coupling glycosyl bromides nonfunctionalized heteroarenes has been described. This strategy features readily available starting materials, mild conditions, good functional group tolerance, and site- stereoselectivities (α-configuration). A variety monosaccharides (d-lyxose, d-ribose, l-arabinose, d-glucose, d-mannose, d-glucuronide, d-fucose), disaccharides (lactose, melibiose, maltose), polysaccharide (maltriose) can couple series heteroarenes, such as purine, benzothiazole, thiazolopyridine, benzoxazole, benzimidazole, imidazopyridine, phenanthridine. Biologically important molecules, theophylline, famciclovir, ribufuranoside, adenine, be glycosylated directly through using this method. Site- rationalized predicted density theory (DFT) calculations.

Language: Английский

Citations

59
Diastereoselective Decarboxylative Alkynylation of Anomeric Carboxylic Acids Using Cu/Photoredox Dual Catalysis DOI
Mingxiang Zhu, Samir Messaoudi

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(10), P. 6334 - 6342

Published: May 12, 2021

Alkynyl C-nucleosides are of high value for various applications; however, their synthesis remains underexplored. Here we report a simple route toward the alkynyl from and stable furanosyl carboxylic acids terminal alkynes under low-cost nontoxic copper catalysis. The approach that here demonstrates power Cu/photoredox dual catalysis to access highly complex glycosides mild conditions.

Language: Английский

Citations

57
Dihydroquinazolinones as adaptative C(sp3) handles in arylations and alkylations via dual catalytic C–C bond-functionalization DOI Creative Commons
Xin‐Yang Lv, Roman Abrams, Rubén Martı́n

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 3, 2022

Abstract C–C bond forming cross-couplings are convenient technologies for the construction of functional molecules. Consequently, there is continual interest in approaches that can render traditionally inert functionality as cross-coupling partners, included this ketones which widely-available commodity chemicals and easy to install synthetic handles. Herein, we describe a dual catalytic strategy utilizes dihydroquinazolinones derived from ketone congeners adaptative one-electron handles forging C( sp 3 ) architectures via α cleavage with aryl alkyl bromides. Our approach achieved by combining flexibility modularity nickel catalysis propensity photoredox events generating open-shell reaction intermediates. This method distinguished its wide scope broad application profile––including chemical diversification advanced intermediates––, providing technique complementary existing reactions operates within bond-functionalization arena.

Language: Английский

Citations

51