1,2-cis-β-Mannopyranoside Formation by the Dimethylphosphinothioate Method

Yamanoi, Takahiro; Nakamura, Kazumi; Takeyama, Hiroshi; Yanagihara, Kenji; Inazu, Toshiyuki

doi:10.1246/cl.1993.343

Cited by 16 publications

(12 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For derivatives of the d -galacto series a remote effect beneficial for the formation of α-galactosides was also noted when a participating moiety was present at C-4. 43 Similar effects (including C-3 participation) were also detected for the derivatives of the l -fuco, 44 l -rhamno, 45 d -manno, 46 and d -gluco 47 series.…”

Section: Effect Of the Glycosyl Donormentioning

confidence: 52%

Stereocontrolled 1,2-cis glycosylation as the driving force of progress in synthetic carbohydrate chemistry

2015

View full text Add to dashboard Cite

show abstract

Section: Effect Of the Glycosyl Donormentioning

confidence: 52%

Stereocontrolled 1,2-cis glycosylation as the driving force of progress in synthetic carbohydrate chemistry

2015

View full text Add to dashboard Cite

show abstract

“…There are several methodologies developed for the synthesis of b-mannopyranosides, 18 particularly the intramolecular aglycon delivery which tethers the glycosyl donor and the acceptor together on the same molecule. 19 Yamanoi and co-workers 20 150-162 Hz (Figure 7). 23 The interest in the preparation of S-glycosides has mainly arisen due to their increased stability towards hydrolysis by glycosidases with the premise that these may produce effective biological agents for the treatment of carcinomas and other disease states.…”

Section: Methodsmentioning

confidence: 96%

Glycosylation Based on Glycosyl Phosphates as Glycosyl Donors

Hariprasad¹,

Jiang²,

Singh³

2002

Synlett

View full text Add to dashboard Cite

Glycosyl phosphates have emerged as useful glycosyl donors for stereoselective glycosidic bond formation in the synthesis of oligosaccharides. In this account, we describe some of our work in developing and further expanding this methodology, particularly with the use of propane-1,3-diyl phosphate as the anomeric leaving group. We have studied the reactions of several glycosyl propane-1,3-diyl phosphates with or without C-2 participating groups with a range of glycosyl acceptors in the presence of trimethylsilyl triflate in either stoichiometric or catalytic amount, and demonstrated their application in the synthesis of several disaccharides and also the synthesis of some trisaccharides.Carbohydrate research has gone through a rapid phase of expansion during the last thirty years, not only because carbohydrates are being considered as extremely useful stereochemical building blocks for complex organic synthesis. 1,2 More importantly, apart from being an energy source in living systems, carbohydrates increasingly are being recognised as playing important roles in a variety of biological processes, such as signaling, cell-cell communication, molecular and cellular targeting. 3 It is the enormous advances in the latter that forms the basis of a new area of multidisciplinary research named glycobiology, which deals mainly with the nature and role of carbohydrates in biological events. In biological systems, although carbohydrates can exist as free monosaccharides and oligosaccharides, the majority are covalently attached to other non-carbohydrate biomolecules, such as proteins or lipids, to form what are called glycoconjugates that generally include glycoproteins, glycolipids and proteoglycans. The advancement of research in glycobiology has to a large extent depended on the technological progress in structural analysis of oligosaccharides in glycoconjugates. However, in order to study the biological functions of carbohydrates and to develop carbohydratebased therapeutic agents, sufficient quantities of pure oligosaccharides and glycoconjugates are often required, and some of these can only be accessed by chemical synthesis. Compared with proteins and nucleic acids, which have linear structures, the construction of oligosaccharides from the monomers is more complicated due to the number of hydroxyl groups available for linkage and also the creation of a-or b-glycosidic bond at the anomeric centre.Since the early glycosylation method reported by Koenigs and Knorr in 1901, 4 stereoselective formation of the glycoside linkage in oligosaccharide synthesis has remained an active area of research. Over the last century, research in glycosylation chemistry has resulted in a better understanding of the glycoside reaction and produced an array of glycosylation methods that generally catered for almost every type of glycosidic bond formation. 5 However, to date, there is still no generally applicable method for glycoside formation as in the case of peptide synthesis. Considering the complex stereoelectronic nature of carbohy...

show abstract

“…Glycosyl dimethylphosphinothioate donors were introduced by Inazu and co-workers in 1985, drawing inspiration from the use of this type of leaving group in peptide synthesis. , It was concluded that silver perchlorate was an efficient activator of these novel glycosyl donors, leading to disaccharides in excess of 69%, although a stoichiometric amount of the promoter was essential for the glycosylations to take place. Inazu and co-workers have since investigated dimethylphosphinothioates very thoroughly as glycosyl donors and found that iodine in combination with trityl perchlorate , was a very efficient activator for these glycosyl donors. Trityl salts such as TrClO 4 , TrBF 4 , and TrSnCl 5 have since proven to be good catalysts for the activation of the dimethylphosphinothioate donors. ,, Years after that, in 2006, Yamanoi and Inazu et al found use of the dimethylphosphinothioate leaving group in glycosylations with 1- C alkylated glycosyl donors .…”

Section: Phosphorus-based Glycosyl Donorsmentioning

confidence: 99%

Catalytic Glycosylations in Oligosaccharide Synthesis

2018

View full text Add to dashboard Cite

Catalytic glycosylation has been a central reaction in carbohydrate chemistry since its introduction by Fischer 125 years ago, but it is only in the past three to four decades that catalytic methods for synthesizing oligosaccharides have appeared. Despite the development of numerous elegant and ingenious catalytic glycosylation methods, only a few are in general use. This review covers all methods of catalytic glycosylation with the focus on the development and application in oligosaccharide synthesis and provide an overview of the scope and limitations of these. The review also includes relevant mechanistic studies of catalytic glycosylations. The future of catalytic glycosylation chemistry is discussed, including specific, upcoming methods and possible directions for the field of research in general.

show abstract

1,2-cis-β-Mannopyranoside Formation by the Dimethylphosphinothioate Method

Abstract: 1,2-cis-β-Mannopyranosides were obtained predominantly by reactions of mannopyranosyl dimethylphosphinothioate derivatives with several alcohols in the presence of iodine and a catalytic amount of triphenylmethyl perchlorate as the activator in benzene.

Cited by 16 publications

References 6 publications

Stereocontrolled 1,2-cis glycosylation as the driving force of progress in synthetic carbohydrate chemistry

Stereocontrolled 1,2-cis glycosylation as the driving force of progress in synthetic carbohydrate chemistry

Glycosylation Based on Glycosyl Phosphates as Glycosyl Donors

Catalytic Glycosylations in Oligosaccharide Synthesis

Contact Info

Product

Resources

About