Ni‐Catalyzed Cross‐Coupling of 2‐Iodoglycals and 2‐Iodoribals with Grignard Reagents: A Route to 2‐<i>C</i>‐Glycosides and 2’‐<i>C</i>‐Nucleosides

Cossy, Janine; Polák, Peter

doi:10.1002/chem.202104311

Cited by 11 publications

(6 citation statements)

References 65 publications

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“…Monofunctionalization of 2-iodoglycals via palladium-catalyzed cross-couplings can thus be considered as the most reliable strategy. For example, monofunctionalization typically involves palladium-catalyzed Heck 7 , Stille 14 , Suzuki–Miyaura 15 , Sonogashira 16 , 17 , aminocarbonylation 18 , alkenylation 19 , alkylation 20 , among others 21 , 22 (Figs. 1, (1), left ).…”

Section: Introductionmentioning

confidence: 99%

Stereoselective assembly of C-oligosaccharides via modular difunctionalization of glycals

Ding,

Xu,

Huang

et al. 2024

Nat Commun

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C-oligosaccharides are found in natural products and drug molecules. Despite the considerable progress made during the last decades, modular and stereoselective synthesis of C-oligosaccharides continues to be challenging and underdeveloped compared to the synthesis technology of O-oligosaccharides. Herein, we design a distinct strategy for the stereoselective and efficient synthesis of C-oligosaccharides via palladium-catalyzed nondirected C1–H glycosylation/C2-alkenylation, cyanation, and alkynylation of 2-iodoglycals with glycosyl chloride donors while realizing the difunctionalization of 2-iodoglycals. The catalysis approach tolerates various functional groups, including derivatives of marketed drugs and natural products. Notably, the obtained C-oligosaccharides can be further transformed into various C-glycosides while fully conserving the stereochemistry. The results of density functional theory (DFT) calculations support oxidative addition mechanism of alkenyl-norbornyl-palladacycle (ANP) intermediate with α-mannofuranose chloride and the high stereoselectivity of glycosylation is due to steric hindrance.

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Section: Introductionmentioning

confidence: 99%

Stereoselective assembly of C-oligosaccharides via modular difunctionalization of glycals

Ding,

Xu,

Huang

et al. 2024

Nat Commun

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“…The introduction of aromatic or heteroaromatic functionalities on the nucleosides (that help enhance the fluorescent properties) via metal-catalyzed cross-coupling reactions [5,6] (especially palladium-catalyzed Suzuki-Miyaura coupling) has been extensively explored [7,8]. Contributions by the research groups of Len [9][10][11][12], Shaughnessy [13][14][15][16], Lakshman [17][18][19][20][21][22] and many others [18][19][20][21][22] are acknowledged for their advances in the area of nucleoside modification. We have also been active in the development of several catalytic systems (palladium-based) allowing efficient cross-coupling [23][24][25][26][27][28][29][30].…”

Section: Introductionmentioning

confidence: 99%

Rapid plugged flow synthesis of nucleoside analogues via Suzuki-Miyaura coupling and heck Alkenylation of 5-Iodo-2’-deoxyuridine (or cytidine)

et al. 2023

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Nucleosides modification via conventional cross-coupling has been performed using different catalytic systems and found to take place via long reaction times. However, since the pandemic, nucleoside-based antivirals and vaccines have received widespread attention and the requirement for rapid modification and synthesis of these moieties has become a major objective for researchers. To address this challenge, we describe the development of a rapid flow-based cross-coupling synthesis protocol for a variety of C5-pyrimidine substituted nucleosides. The protocol allows for facile access to multiple nucleoside analogues in very good yields in a few minutes compared to conventional batch chemistry. To highlight the utility of our approach, the synthesis of an anti-HSV drug, BVDU was also achieved in an efficient manner using our new protocol.

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“…Monofunctionalization of 2-iodoglycals via palladium-catalyzed cross-couplings can thus be considered as the most reliable strategy. For example, monofunctionalization thuas far typically involved Heck, 7 Stille, 14 Suzuki-Miyaura, 15 Sonogashira, [16][17] aminocarbonylation, 18 alkenylation, [19][20] among others [21][22] (Fig. 1a, left).…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Assembly of C-oligosaccharides via Modular Difunctionalization of Glycals

Liang,

Ding,

et al. 2023

Preprint

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C-oligosaccharides are found in natural products and drug molecules. Despite the considerable progress made during the last decades, modular and stereoselective synthesis of C-oligosaccharides continues to be challenging and underdeveloped compared to the synthesis technology of O-oligosaccharides. Herein, we have designed a distinct strategy for the stereoselective and efficient synthesis of C-oligosaccharides via palladium-catalyzed nondirected C1-H glycosylation/C2-alkenylation, cyanation, and alkynylation of 2-iodoglycals with glycosyl chloride donors while realizing the difunctionalization of 2-iodoglycals for the first time. The catalysis approach tolerates various functional groups, including derivatives of marketed drugs and natural products. Notably, the obtained C-oligosaccharides can be further transformed into various C-glycosides while fully conserving the stereo-chemistry. Density functional theory (DFT) calculations studies are supportive of a concerted oxidative addition mechanism alkenyl-norbornadiene-palladacycle (ANP) intermediate with an α-mannofuranose chloride and the high stereoselectivity of glycosylation was due to steric hindrance.

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Ni‐Catalyzed Cross‐Coupling of 2‐Iodoglycals and 2‐Iodoribals with Grignard Reagents: A Route to 2‐C‐Glycosides and 2’‐C‐Nucleosides

Cited by 11 publications

References 65 publications

Stereoselective assembly of C-oligosaccharides via modular difunctionalization of glycals

Stereoselective assembly of C-oligosaccharides via modular difunctionalization of glycals

Rapid plugged flow synthesis of nucleoside analogues via Suzuki-Miyaura coupling and heck Alkenylation of 5-Iodo-2’-deoxyuridine (or cytidine)

Stereoselective Assembly of C-oligosaccharides via Modular Difunctionalization of Glycals

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