Programmable reactivity-based one-pot oligosaccharide synthesis

Lee, Jinq‐Chyi; Greenberg, William A.; Wong, Chi‐Huey

doi:10.1038/nprot.2006.489

Cited by 67 publications

(49 citation statements)

References 12 publications

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“…Clearly, iterative one-pot glycosylation for oligosaccharide synthesis could improve the synthetic efficiency by obviating some time-consuming purification processes. 26–28 Thus, after three sequential glycosylation steps, 3 was obtained in 6 h and a 39% overall yield, giving an average of more than 73% yield for each glycosylation step. All of the reactions were proved α-specific (anomeric 1 J C,H values of 3 were between 169 and 176 Hz).…”

Section: Resultsmentioning

confidence: 98%

Synthesis of a Tristearoyl Lipomannan via Preactivation-Based Iterative One-Pot Glycosylation

Gao

Guo

2013

J. Org. Chem.

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A convergent and efficient strategy was developed for the synthesis of lipomannan (LM), useful for vaccine development. Thioglycosides were employed as glycosyl donors to construct two key pseudotrisaccharide and tetramannose intermediates through pre-activation-based glycosylation strategy. These building blocks were then successfully coupled to form the LM core, which was lapidated, phospholipidated, and finally globally deprotected to afford the target molecule. The intermediate LM core involved in this synthesis contained orthogonal protections, which would facilitate its variable modifications for the preparation of other complex LM derivatives and for the synthesis of LM conjugates as LM-based vaccines.

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Section: Resultsmentioning

confidence: 98%

Synthesis of a Tristearoyl Lipomannan via Preactivation-Based Iterative One-Pot Glycosylation

Gao

Guo

2013

J. Org. Chem.

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“…To a 50 mL round-bottom flask were added the tetraacetate 5 13 (1.11 g, 2.28 mmol) and a 2:3 mixture of MeOH-CH 2 Cl 2 (25 mL). The mixture was cooled to 0 °C, treated with a 0.5 M NaOMe solution in MeOH (1.50 mL, 0.75 mmol) and stirred for 10 minutes followed by warming up to room temperature and further stirring for 2 hours.…”

Section: Methodsmentioning

confidence: 99%

“…Similarly, a database was established by the Wong group tabulating Relative Reactivity Values (RRVs) of thiotolyl building blocks glycosylating methanol 2, 11. RRV methanol values have been employed as a quantitative measure to guide the design of building blocks with requisite anomeric reactivities for reactivity based chemoselective glycosylation, as applied in assemblies of several complex oligosaccharides 2, 10, 11, 13-15. Generally, minimum ten-fold difference in RRVs methanol between the two competing building blocks is desired so that theoretically greater than 90% glycosylation yield can be obtained.…”

Section: Introductionmentioning

confidence: 99%

Thio-arylglycosides with various aglyconpara-substituents: a probe for studying chemical glycosylation reactions

Huang

et al. 2009

Org. Biomol. Chem.

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Summary Three series of thioglycosyl donors differing only in their respective aglycon substituents within each series have been prepared as representatives of typical glycosyl donors. The relative anomeric reactivities of these donors were quantified under competitive glycosylation conditions with various reaction time, promoters, solvents and acceptors. Over three orders of magnitude reactivity difference were generated by simple transformation of the para-substituent on the aglycon with methanol as the acceptor, while chemoselectivities became lower with carbohydrate acceptors. Excellent linear correlations were attained between relative reactivity values of donors and σp values of the substituents in the Hammett plots. This indicates that the glycosylation mechanism remains the same over a wide range of reactivities and glycosylation conditions. The negative slopes of the Hammett plots suggested that electron donating substituents expedite the reactions and the magnitudes of slopes can be rationalized by neighboring group participation as well as electronic properties of the glycon protective groups. Within the same series of donors, less nucleophilic acceptors gave smaller slopes in their Hammett plots. This is consistent with the notion that acceptor nucleophilic attack onto the reactive intermediate is part of the rate limiting step of the glycosylation reaction. Excellent linear Hammett correlations were obtained between relative reactivity values of three series of donors differing only in their aglycon substituents and σp values of the substituents.

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“…The major concern with glycans is that the synthesis of ultrapure synthetic glycans has been time consuming and labor intensive in the past. However, novel methodologies such as solid-phase, one-pot, and solidphase and enzyme-based technologies have significantly alleviated the problem of rapid production of glycans [126][127][128][129][130]. Also, glycans are ubiquitous and, therefore, can be "thought" to be lacking selectivity.…”

Section: Carbohydrate-based Detectionmentioning

confidence: 99%

Molecular Recognition Elements for Toxin and Pathogen Detection

2011

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Rapid, sensitive, and selective detection of infectious agents in food, water, the environment, and patient samples is critical for appropriate countermeasures, particularly in the event of a suspected outbreak. The biosensors should be inexpensive, portable, and easy to use, require minimal sample preparation and reagents, and should be able to detect emerging variants for wide acceptance. The vast number of biological threats, each with its own unique characteristics, as well as the stringent requirements of a biosensor, dictates a multidisciplinary approach to overcome the scientific and technological hurdles necessary to develop a "real-time" biosensor. While advances in several areas are required, one of the most critical components of a biosensor is the recognition molecule. Ultimately, the success of a biosensor is highly dependent on the specificity, sensitivity, reproducibility, and broad applicability of the recognition element. In this chapter, we review the state-of-the-art advancements in the molecular recognition of toxins and pathogens. We discuss different recognition molecules in detail with particular emphasis on the use of emerging recognition molecules that include antimicrobial peptides, carbohydrates, molecularly imprinted polymers, aptamers, and phage for detection of infectious agents. As this chapter indicates, there are advantages and limitations to each molecule. However, significant advances in the area of molecular recognition for toxins and pathogens are being made. As the field evolves, continued improvements in molecular recognition and other components of the biosensor such as transducer Chemosensors: Principles, Strategies, and Applications, First Edition. Edited by Binghe Wang and Eric V. Anslyn.

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Programmable reactivity-based one-pot oligosaccharide synthesis

Cited by 67 publications

References 12 publications

Synthesis of a Tristearoyl Lipomannan via Preactivation-Based Iterative One-Pot Glycosylation

Synthesis of a Tristearoyl Lipomannan via Preactivation-Based Iterative One-Pot Glycosylation

Thio-arylglycosides with various aglyconpara-substituents: a probe for studying chemical glycosylation reactions

Molecular Recognition Elements for Toxin and Pathogen Detection

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