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

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

Felix Kallert

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(15), С. 11532 - 11544

Опубликована: Июль 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.

Язык: Английский

Процитировано

5
Tetrafluoropyridin-4-yl thioglycosides (TFPTGs): Versatile donors in C-, O-, and N-glycosidic construction DOI
Hong Cao, Hui Liu,

Jin‐Xi Liao

и другие.

Tetrahedron Letters, Год журнала: 2025, Номер 160, С. 155563 - 155563

Опубликована: Март 31, 2025

Язык: Английский

Процитировано

0
Exploration of thioglycosides in photoinduced desulfurative cross-coupling reactions DOI Creative Commons
Ji Zhang, Qi Liu,

Angus Chiang

и другие.

Опубликована: Июнь 5, 2024

Thioglycosides have been a mainstay of O-glycosylation chemistry. Here we demonstrate that under mild photochemical conditions, readily synthesized bench-stable electron poor thioglycosides are also useful C-glycoside precursors, undergoing desulfurative glycosyl radical generation. Two complementary classes described. The dithioimidocarbonates, undergo coupling in the presence 4CzIPN, weak acid and Hantzsch ester, blue light illumination. Alternatively, 4-cyanotetrafluorophenyl or 4-tetrafluropyridyl can be used to generate radicals base ester irradiation catalyst-free approach. These perform well Geise-like reactions yield C-glycosides with high stereoselectivity. Furthermore, related thioethers bearing groups potent precursors.

Язык: Английский

Процитировано

3
Merging radical catalysis and noncovalent stereocontrol concepts to forge native O-glycosidic linkages DOI
Hao Guo, Charles C. J. Loh

Science Bulletin, Год журнала: 2024, Номер 69(21), С. 3308 - 3310

Опубликована: Авг. 30, 2024

Язык: Английский

Процитировано

1
Taming glycosylidene carbenes through bench-stable glycosylidene diaziridines to access boro-ketosides DOI Creative Commons
Charles C. J. Loh

Chem Catalysis, Год журнала: 2024, Номер 4(4), С. 100980 - 100980

Опубликована: Апрель 1, 2024

Язык: Английский

Процитировано

0
Stereoselective Synthesis of 2-Deoxy-α-N-Glycosides from Glycals with 1,4,2-Dioxazol-5-ones DOI Open Access

Zhenpeng Shen,

Guoyin Yin,

Yangyang Li

и другие.

Authorea (Authorea), Год журнала: 2024, Номер unknown

Опубликована: Май 6, 2024

The synthesis of N-glycosides has received significant attention due to their crucial role in carbohydrate chemistry. Despite considerable advancements were developed the construction N-glycosides, methods for stereoselective 2-deoxy-α-N-glycosides are still limited. Herein, we disclosed a nickel-catalyzed hydroamination glycals under mild conditions. This transformation could allow an array with excellent α-stereoselectivity. Nickel-catalyzed glycosylation reactions, particularly those involving anomeric C(sp3)-metal bond formation, have proven be effec-tive and strategy producing various N-glycosides. Additionally, highlight application this reaction, γ-sugar amino acid derivatives synthesized by one step.

Язык: Английский

Процитировано

0
“Cap and glycosylate” strategy for direct radical functionalization of native sugars DOI
Hiroaki Matoba, Go Hirai

Science Bulletin, Год журнала: 2024, Номер 69(20), С. 3163 - 3165

Опубликована: Авг. 14, 2024

Язык: Английский

Процитировано

0
Photocatalyst-free light-promoted carbohydrate synthesis and modification DOI
Jing Wang,

Fan Zhou,

Yu‐Ping Xu

и другие.

Carbohydrate Research, Год журнала: 2024, Номер 546, С. 109304 - 109304

Опубликована: Ноя. 5, 2024

Язык: Английский

Процитировано

0
Copper/photoredox catalysis enables desulfonylative radical N-glycosylation DOI Creative Commons
Qikai Sun,

Quanquan Wang,

Wenzhuo Qin

и другие.

Опубликована: Ноя. 20, 2023

The state-of-the-art for glycosylation primarily relies on the classical polar reactions of heteroatomic nucleophiles with electrophilic glycosyl oxocarbenium intermediates. While such an ionic strategy has worked well to deliver O-glycosides, its utilization in N-glycoside synthesis is often plagued by subdued reactivity N-nucleophiles under acidic reaction conditions required activating donors. Exploring radical intermediates could open up new pathways. However, despite recent significant progress radical-mediated C-glycosides, harnessing radicals generation canonical O- or N-glycosides remains elusive. Herein, we report first examples N-glycosylation using readily accessible sulfone donors and mild copper-catalyzed photoredox-promoted conditions. method efficient, selective, redox-neutral, broadly applicable, enabling facile access a variety complex nucleosides streamlined fashion. Importantly, present system tolerates presence water offers unique chemoselectivity, allowing selective NH sites over hydroxyl groups that would otherwise pose challenges conventional cationic N-glycosylation.

Язык: Английский

Процитировано

1
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