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A Survey of Ley’s Reactivity Tuning in Oligosaccharide Synthesis

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Reactivity Tuning in Oligosaccharide Assembly

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 301))

Abstract

This chapter summarizes the concepts and chemistry developed by Ley’s group in relation to the relevance of reactivity tuning in oligosaccharide coupling reactions. The recognition that protecting groups affect the reactivity of glycosyl donors allowed Ley’s group to make imaginative use of their 1,2-diacetal protecting groups. The combination of 1,2-diacetals with the presence of different anomeric leaving groups provides up to four different levels of reactivity. The exploitation of these reactivity levels in chemoselective glycosylation processes (reactivity tuning) has allowed the development of highly simplified routes to several complex oligosaccharides in step-wise or one-pot procedures.

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Abbreviations

Aloc:

Allyloxycarbonyl

BDA:

Butane-2,3-diacetals

bis-DHP:

3.3′,4.4′-Tetrahydro-6,6′-bis-2H-pyran

Bn:

Benzyl (CH2Ph)

Boc:

tert-Butoxycarbonyl

Bz:

Benzoyl

Cbz:

Benzyloxycarbonyl

CDA:

Cyclohexane-1,2-diacetals

CSA:

Camphorsulfonic acid

DF:

Deactivation factor

Dispoke:

Dispiroketal

FBn:

p-Fluorobenzyl

gp:

Glycoprotein

GPI:

Glycosylphosphatidylinositol

HIV:

Human immunodeficiency virus

HPLC:

High pressure liquid chromatography

IDCP:

Iodonium dicollidine perchlorate

NIS:

N-Iodosuccinimide

RRV:

Relative reactivity values

SN2:

Bimolecular nucleophilic substitution

TBAF:

Tetra-n-butyl ammonium fluoride

TBDPS:

tert-Butyldiphenylsilyl

TBS:

tert-Butyldimethylsilyl

TESOTf:

Triethylsilyltrifluoromethanesulfonate

TFA:

Trifluoromethanesulfonic acid

TfOH:

Triflic acid

TMB:

2,2,3,3-Tetramethoxybutane

TMC:

1,1,2,2-Tetramethoxycyclohexane

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Authors and Affiliations

  1. Instituto de Química Orgánica General (CSIC), Juan de la Cierva 3, 28006, Madrid, Spain

    Ana M. Gómez

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  1. Ana M. Gómez
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Correspondence to Ana M. Gómez .

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Editors and Affiliations

  1. Natural Products and Glycotechnology Res, Swarthmore Road 4118, Durham, 27706, North Carolina, USA

    Bert Fraser-Reid

  2. Instituto de Quimica Orgánica General (C, Juan de la Cierva 3, Madrid, 28006, Spain

    J. Cristóbal López

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Gómez, A.M. (2010). A Survey of Ley’s Reactivity Tuning in Oligosaccharide Synthesis. In: Fraser-Reid, B., Cristóbal López, J. (eds) Reactivity Tuning in Oligosaccharide Assembly. Topics in Current Chemistry, vol 301. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2010_112

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