Glycosylation via remote activation of anomeric leaving groups: development of 2-(2-propylsulfinyl)benzyl glycosides as novel glycosyl donors

Shu, Penghua; Yao, Wang; Xiao, Xiong; Sun, Jiuchang; Zhao, Xin; Zhao, Yueqi; Xu, Yang; Tao, Jinyi; Yao, Guangmin; Zeng, Jing; Wan, Qian

doi:10.1039/c5qo00359h

Cited by 31 publications

(5 citation statements)

References 72 publications

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“…Importantly, hydroxysulfoxide 131 can be recovered after the reaction in 92% yield and can thereafter be recycled. Later, a detailed optimization of the sulfoxide unit and more applications of this reaction were reported, 76,77 and recently the use of sulfoxides in carbohydrate synthesis has been reviewed. 78,79 Several groups have used the interrupted Pummerer reaction for the sulfanylation of arenes.…”

Section: Sulfoxides 21 Pummerer Reactionsmentioning

confidence: 99%

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

et al. 2019

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Organosulfur compounds have long played a vital role in organic chemistry and in the development of novel chemical structures and architectures. Prominent among these organosulfur compounds are those involving a sulfur(IV) center, which have been the subject of countless investigations over more than a hundred years. In addition to a long list of textbook sulfur-based reactions, there has been a sustained interest in the chemistry of organosulfur(IV) compounds in recent years. Of particular interest within organosulfur chemistry is the ease with which the synthetic chemist can effect a wide range of transformations through either bond formation or bond cleavage at sulfur. This review aims to cover the developments of the past decade in the chemistry of organic sulfur(IV) molecules and provide insight into both the wide range of reactions which critically rely on this versatile element and the diverse scaffolds that can thereby be synthesized.

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Section: Sulfoxides 21 Pummerer Reactionsmentioning

confidence: 99%

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

et al. 2019

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“…With latent SPTB glycosides 19a – j in hand, we began to investigate selective oxidation of the phenyl thioethers. In our previous work, we demonstrated that OPTB glycoside could be selectively oxidized to the corresponding OPSB glycosyl donor, leaving an S -methyl group intact by PIFA (1.2 equiv) . Although it is a daunting task to differentiate a phenyl thioether group from an anomeric methyl thioether group, we were delighted to find that the desired SPSB glycosides 2a – j could be prepared smoothly by selective oxidation with PIFA or m -CPBA…”

Section: Resultsmentioning

confidence: 99%

“…We revealed that the LG was remotely activated by an interrupted Pummerer reaction. − Despite significant progress, only armed and superarmed glycosyl donors bearing the oxidized O -benzyl LG can be successfully activated to unleash the desired oxocarbenium. In contrast, the disarmed glycosides usually yield unproductive side products: intermolecular Pummerer reaction adducts …”

Section: Introductionmentioning

confidence: 99%

Remote Activation of Disarmed Thioglycosides in Latent-Active Glycosylation via Interrupted Pummerer Reaction

et al. 2016

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S-glycosides, S-2-(2-propylthio)benzyl (SPTB) glycosides, were converted to the corresponding oxidized glycosyl donors, S-2-(2-propylsulfinyl)benzyl (SPSB) glycosides, by simple and selective oxidation. Treatment of disarmed SPSB donor and various acceptors with triflic anhydride provided the desired glycosides in good to excellent yields. Meanwhile, observation of thiosulfinate, thiosulfonate, and disulfide suggested that the leaving group was activated via an interrupted Pummerer reaction. The disarmed SPSB thioglycosyl donors could be selectively activated in the presence of various thioglycosides with remote activation mode. Finally, two natural hepatoprotective glycosides, Leonoside E and Leonuriside B, were efficiently synthesized in a convergent manner with this newly developed method.

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“…Unfortunately, screening of these donors under various reaction conditions with different activators such as Tf 2 O, Ac 2 O, TFAA, etc., produced disappointing results. 18 In most cases, no desired glycosylation occurred and the major side reactions were intermolecular Pummerer reactions and…”

Section: Syn Lettmentioning

confidence: 99%

Interrupted Pummerer Reaction in Latent/Active Glycosylation

Meng

Zeng

Wan

2017

Synlett

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A latent/active glycosylation strategy is efficient for rapid assembly of oligosaccharides. We recently developed novel OPTB/OPSB and SPTB/SPSB glycosides as two pairs of latent/active glycosyl donors. The active OPSB and SPSB glycosyl donors are efficiently activated by Tf2O via an interrupted Pummerer reaction mechanism. In this account, the design, developments, mechanism studies and applications of these new glycosylation methodologies are described.1 Introduction2 Conceiving Ideas3 Synthesis of OPSB and SPSB Glycosides4 Substrate Scope5 Application in the Synthesis of Natural Products6 Conclusion

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Glycosylation via remote activation of anomeric leaving groups: development of 2-(2-propylsulfinyl)benzyl glycosides as novel glycosyl donors

Abstract: New glycosyl donors with recyclable and regenerable leaving groups, which could be activated via remote mode, were designed for latent-active glycosylation.

Cited by 31 publications

References 72 publications

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Remote Activation of Disarmed Thioglycosides in Latent-Active Glycosylation via Interrupted Pummerer Reaction

Interrupted Pummerer Reaction in Latent/Active Glycosylation

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