Hirao Cross-Coupling Reaction as an Efficient Tool to Build Non-natural C2-Phosphonylated Sugars

Monasson, Olivier; Malinowski, Maciej; Lubin-Germnain, Nadége; Ferry, Angélique

doi:10.1055/a-1709-3305

Cited by 5 publications

(4 citation statements)

References 36 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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“…[35,36] Since the discovery of a smooth route to 2iodoglycals, [37] the metal catalysed methodologies became easily available to functionalise C-2 position of glycals and therefore possibly towards the synthesis of complex hybrids. [38][39][40][41][42][43][44][45][46][47][48] However, apart from click chemistry strategy, [49][50][51][52][53][54][55][56] the great utility of metal catalysis, has not been fully explored in glycoporphyrin chemistry.…”

Section: Introductionmentioning

confidence: 99%

Suzuki‐Miyaura Reaction of Glycals with Base‐Labile Protecting Groups as a New Route to Glycoporphyrins

Godlewski,

Malinowski

2024

Adv Synth Catal

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Glycoporphyrins are considered promising photosensitisers of new generation. Herein, we describe the original, metal‐catalysed method towards porphyrin‐carbohydrate C‐C conjugates. The protocol of Suzuki‐Miyaura reaction has been developed and it was compatible with peracetylated 2‐iodoglycals. The utility of the reaction was exemplified on 15 different (C‐2)‐arylated sugar derivatives. Then it was applied on more challenging starting materials, namely, porphyrin boronates in which we addressed the issues of difficult transmetalation step usually observed on palladium‐catalysed processes of porphyrin derivatives. The efficiency of the protocol was finally applied to synthesize the library of glycoporphyrins proving the versatile character of this strategy. Keywords: Suzuki‐Miyaura reaction, glycoporphyrins, photosensitisers, carbohydrates, porphyrins, palladium catalysis, glycal

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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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Hirao Cross-Coupling Reaction as an Efficient Tool to Build Non-natural C2-Phosphonylated Sugars

Cited by 5 publications

References 36 publications

Stereoselective assembly of C-oligosaccharides via modular difunctionalization of glycals

Stereoselective assembly of C-oligosaccharides via modular difunctionalization of glycals

Suzuki‐Miyaura Reaction of Glycals with Base‐Labile Protecting Groups as a New Route to Glycoporphyrins

Stereoselective Assembly of C-oligosaccharides via Modular Difunctionalization of Glycals

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