228
2
General Synthetic Methods
4.4
Rearrangement Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
4.4.1 1,2-Migrations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
4.4.2 Rearrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
5
Introduction of Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
5.1
Nucleophilic Substitutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
5.2
Ring-Opening Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
5.3
Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5.3.1 Addition to Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5.3.2 Addition to Isolated Double Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
5.4
Coupling Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
Abstract
Saccharides derived with a variety of functional groups are usually of great importance in many
biological and chemical aspects. The chemical modifications of saccharides with heteroatoms
at nonanomeric positions are reviewed in this chapter.
Keywords
Halogens; Nitrogen; Sulfur; Phosphorus; Nucleophilic substitution; Ring-opening; Addition
reaction
Abbreviations
AIBN
azo-bis-isobutyronitrile
CAN
ceric ammonium nitrate
DAST diethylaminosulfur trifluoride
DBU
1,8-diazabicyclo[5.4.0]undec-7-ene
DEAD diethyl azodicarboxylate
DFMBA N,N-diethyl-α,α-difluoro-(m-methylbenzyl)amine
DIAD
diisopropyl azodicarboxylate
dppb
1,4-bis(diphenylphosphino)butane
IDCP
iodonium di-sym-collidine perchlorate
IBX
1-hydroxy-1,2-benziodoxol-3(1H)-one 1-oxide
NBS
N-bromosuccinimide
PMB
p-methoxybenzyl
SMDA sodium dihydrobis(2-methoxyethoxy)aluminate
TASF
tri(dimethylamino)-sulfonium difluorotrimethylsilicate
TFAA trifluoroacetic anhydride
1 Introduction
The sugar molecule can be considered as a playground for exploratory organic synthesis, and
many functional group manipulations can be carried out on the nonanomeric carbons of carbo-
2
General Synthetic Methods
4.4
Rearrangement Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
4.4.1 1,2-Migrations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
4.4.2 Rearrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
5
Introduction of Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
5.1
Nucleophilic Substitutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
5.2
Ring-Opening Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
5.3
Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5.3.1 Addition to Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
5.3.2 Addition to Isolated Double Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
5.4
Coupling Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
Abstract
Saccharides derived with a variety of functional groups are usually of great importance in many
biological and chemical aspects. The chemical modifications of saccharides with heteroatoms
at nonanomeric positions are reviewed in this chapter.
Keywords
Halogens; Nitrogen; Sulfur; Phosphorus; Nucleophilic substitution; Ring-opening; Addition
reaction
Abbreviations
AIBN
azo-bis-isobutyronitrile
CAN
ceric ammonium nitrate
DAST diethylaminosulfur trifluoride
DBU
1,8-diazabicyclo[5.4.0]undec-7-ene
DEAD diethyl azodicarboxylate
DFMBA N,N-diethyl-α,α-difluoro-(m-methylbenzyl)amine
DIAD
diisopropyl azodicarboxylate
dppb
1,4-bis(diphenylphosphino)butane
IDCP
iodonium di-sym-collidine perchlorate
IBX
1-hydroxy-1,2-benziodoxol-3(1H)-one 1-oxide
NBS
N-bromosuccinimide
PMB
p-methoxybenzyl
SMDA sodium dihydrobis(2-methoxyethoxy)aluminate
TASF
tri(dimethylamino)-sulfonium difluorotrimethylsilicate
TFAA trifluoroacetic anhydride
1 Introduction
The sugar molecule can be considered as a playground for exploratory organic synthesis, and
many functional group manipulations can be carried out on the nonanomeric carbons of carbo-