Programmable selective acylation of saccharides mediated by carbene and boronic acid

Lv, Wenxin; Chen, Hang; Zhang, Xinglong; Ho, Chang Chin; Liu, Yingguo; Wu, Shuquan; Wang, Haiqi; Jin, Zhichao; Robin, Yonggui

doi:10.1016/j.chempr.2022.04.019

Cited by 21 publications

(27 citation statements)

References 51 publications

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“…An unresolved gap in this field pertains to the majority of currently developed chiral catalytic systems for this purpose being still limited to chiral copper complexes and organocatalysis (Fig. 1a) [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] , despite the overwhelming number of examples of asymmetric transition-metal complexes available for enantioselective catalysis. This severely limits selective bond-forming opportunities for carbohydrate functionalizations.…”

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confidence: 99%

A synergistic Rh(I)/organoboron-catalysed site-selective carbohydrate functionalization that involves multiple stereocontrol

et al. 2022

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Site-selective functionalization is a core synthetic strategy that has broad implications in organic synthesis. Particularly, exploiting chiral catalysis to control site selectivity in complex carbohydrate functionalizations has emerged as a leading method to unravel unprecedented routes into biologically relevant glycosides. However, robust catalytic systems available to overcome multiple facets of stereoselectivity challenges to this end still remain scarce. Here we report a synergistic chiral Rh(I)- and organoboron-catalysed protocol, which enables access into synthetically challenging but biologically relevant arylnaphthalene glycosides. Our method depicts the employment of chiral Rh(I) catalysis in site-selective carbohydrate functionalization and showcases the utility of boronic acid as a compatible co-catalyst. Crucial to the success of our method is the judicious choice of a suitable organoboron catalyst. We also determine that exquisite multiple aspects of stereocontrol, including enantio-, diastereo-, regio- and anomeric control and dynamic kinetic resolution, are concomitantly operative.

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confidence: 99%

A synergistic Rh(I)/organoboron-catalysed site-selective carbohydrate functionalization that involves multiple stereocontrol

et al. 2022

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“…There is considerable progress in the use of partially protected monosaccharides in combination with additives such as boronic acids, borinic acids and organotin reagents. 52 These additives are used either to temporarily protect hydroxyl groups or to selectively activate hydroxy groups. This can be viewed as a special case of site-selective modification.…”

Section: Discussionmentioning

confidence: 99%

“…Glycosidic bond formation is at the heart of carbohydrate synthesis and performing this with partly protected monosaccharides is both challenging and important. There is considerable progress in the use of partially protected monosaccharides in combination with additives such as boronic acids, borinic acids and organotin reagents . These additives are used either to temporarily protect hydroxyl groups or to selectively activate hydroxy groups.…”

Section: Discussionmentioning

confidence: 99%

Site-Selective Modification of (Oligo)Saccharides

Witte

Minnaard

2022

ACS Catal.

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Oligosaccharides, either as such or as part of glycolipids, glycopeptides, or glycoproteins, are ubiquitous in nature and fulfill important roles in the living cell. Also in medicine and to some extent in materials, oligosaccharides play an important role. In order to study their function, modifying naturally occurring oligosaccharides, and building in reactive groups and reporter groups in oligosaccharides, are key strategies. The development of oligosaccharides as drugs, or vaccines, requires the introduction of subtle modifications in the structure of oligosaccharides to optimize efficacy and, in the case of antibiotics, circumvent bacterial resistance. Provided the natural oligosaccharide is available, site-selective modification is an attractive approach as total synthesis of the target is often very laborious. Researchers in catalysis areas, such as transition-metal catalysis, enzyme catalysis, organocatalysis, and photoredox catalysis, have made considerable progress in the development of site-selective and late-stage modification methods for mono- and oligosaccharides. It is foreseen that the fields of enzymatic modification of glycans and the chemical modification of (oligo)saccharides will approach and potentially meet each other, but there is a lot to learn and discover before this will be the case.

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“…Besides their most studied interactions with aldehydes or carboxylic acid derivatives, 2 NHCs have also shown remarkable catalytic activity in reactions with imines, 3 silanes, 4 borate esters, 5 etc . 6 To date, investigating new modes of NHC organocatalysis has remained one of the most important tasks in this area. In this work, we discovered an unprecedented activation mode wherein an NHC could directly activate the C(sp 3 )–Cl bond of a chlorinated solvent to realize benzyne chlorination.…”

Section: Introductionmentioning

confidence: 99%

Carbene catalyzed C(sp³)–Cl activation of chlorinated solvents for benzyne chlorination

et al. 2022

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Programmable selective acylation of saccharides mediated by carbene and boronic acid

Cited by 21 publications

References 51 publications

A synergistic Rh(I)/organoboron-catalysed site-selective carbohydrate functionalization that involves multiple stereocontrol

A synergistic Rh(I)/organoboron-catalysed site-selective carbohydrate functionalization that involves multiple stereocontrol

Site-Selective Modification of (Oligo)Saccharides

Carbene catalyzed C(sp³)–Cl activation of chlorinated solvents for benzyne chlorination

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Programmable selective acylation of saccharides mediated by carbene and boronic acid

Cited by 21 publications

References 51 publications

A synergistic Rh(I)/organoboron-catalysed site-selective carbohydrate functionalization that involves multiple stereocontrol

A synergistic Rh(I)/organoboron-catalysed site-selective carbohydrate functionalization that involves multiple stereocontrol

Site-Selective Modification of (Oligo)Saccharides

Carbene catalyzed C(sp3)–Cl activation of chlorinated solvents for benzyne chlorination

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Carbene catalyzed C(sp³)–Cl activation of chlorinated solvents for benzyne chlorination