376
2
General Synthetic Methods
Abstract
This section deals with recent reports concerning degradation and rearrangement reactions of
free sugars as well as some glycosides. The transformations are classified in chemical and
enzymatic ways. In addition, the Maillard reaction will be discussed as an example of degradation and rearrangement transformation and its application in current research in the fields of
chemistry and biology.
Keywords
Degradation; Rearrangement; Hydrolysis; Double bond shift; Ring transformation; Ringcontraction; Ring-expansion; Ferrier carbocyclization; Anomerization; Aromatization;
Maillard reaction; Amadori reaction
Abbreviations
AGEs
advanced glycation end products
DAST
diethylaminosulfur trifluoride
DMDO dimethyldioxirane
DMF
dimethylformamide
EFC
ethanol-from-cellulose
HFIP
1,1,1,3,3,3-hexafluoro-2-propanol
HMF
5-(hydroxymethyl)-2-furaldehyde, 5-hydroxymethylfuraldehyde
IDCP
iodonium dicollidine perchlorate
LTMP
lithium 2,2,6,6-tetramethylpiperidide
m-CPBA 3-chloroperoxybenzoic acid, meta-chloroperoxybenzoic acid
PTC
phase transfer catalysis
TASF
tris(dimethylamino)sulfonium difluorotrimethylsilicate
TMSCN trimethylsilyl cyanide
TMSOTf trimethylsilyl triflate
TMU
N,N-tetramethylurea
1 Overview
Degradation and rearrangement reactions in carbohydrate chemistry are described in the standard organic chemistry textbooks [1,2]. Recent books [3,4,5] contain informative surveys of
developments in this area. This chapter dealing with degradation and rearrangement reactions
of carbohydrate systems covers literature published in the last few years. Degradation reactions are classified into two main categories: hydrolysis from glycosides or polysaccharides
into free sugars, and the degradations from free sugars into useful building blocks or chiral
synthons for organic synthesis. The rearrangement reactions described herein are classified
into four groups: double bond shifts, ring rearrangements associating with a double bond,
ring isomerizations (contraction and expansion), and other processes. Current results on the
Maillard reaction initiated by the Amadori reaction, which are so intimately associated with
degradation and rearrangement reactions, are also discussed in this chapter.
2
General Synthetic Methods
Abstract
This section deals with recent reports concerning degradation and rearrangement reactions of
free sugars as well as some glycosides. The transformations are classified in chemical and
enzymatic ways. In addition, the Maillard reaction will be discussed as an example of degradation and rearrangement transformation and its application in current research in the fields of
chemistry and biology.
Keywords
Degradation; Rearrangement; Hydrolysis; Double bond shift; Ring transformation; Ringcontraction; Ring-expansion; Ferrier carbocyclization; Anomerization; Aromatization;
Maillard reaction; Amadori reaction
Abbreviations
AGEs
advanced glycation end products
DAST
diethylaminosulfur trifluoride
DMDO dimethyldioxirane
DMF
dimethylformamide
EFC
ethanol-from-cellulose
HFIP
1,1,1,3,3,3-hexafluoro-2-propanol
HMF
5-(hydroxymethyl)-2-furaldehyde, 5-hydroxymethylfuraldehyde
IDCP
iodonium dicollidine perchlorate
LTMP
lithium 2,2,6,6-tetramethylpiperidide
m-CPBA 3-chloroperoxybenzoic acid, meta-chloroperoxybenzoic acid
PTC
phase transfer catalysis
TASF
tris(dimethylamino)sulfonium difluorotrimethylsilicate
TMSCN trimethylsilyl cyanide
TMSOTf trimethylsilyl triflate
TMU
N,N-tetramethylurea
1 Overview
Degradation and rearrangement reactions in carbohydrate chemistry are described in the standard organic chemistry textbooks [1,2]. Recent books [3,4,5] contain informative surveys of
developments in this area. This chapter dealing with degradation and rearrangement reactions
of carbohydrate systems covers literature published in the last few years. Degradation reactions are classified into two main categories: hydrolysis from glycosides or polysaccharides
into free sugars, and the degradations from free sugars into useful building blocks or chiral
synthons for organic synthesis. The rearrangement reactions described herein are classified
into four groups: double bond shifts, ring rearrangements associating with a double bond,
ring isomerizations (contraction and expansion), and other processes. Current results on the
Maillard reaction initiated by the Amadori reaction, which are so intimately associated with
degradation and rearrangement reactions, are also discussed in this chapter.