Sugar-pendant diamines.
A set of 1,3-propanediamine derivatives connected to carbohydrates (5) has been prepared in four steps from peracetylated sugar and 1,3-dibromo-2-propanol in 60-73% yields. D-Glucose, D-mannose, D-galactose, D-xylose, D-ribose, and maltose are utilized as sugar molecules in this work. The diamine moiety was connected to the C1 carbon of the glycopyranose ring via an O-glycoside bond. All of the anomeric configurations and sugar puckering conformations, except in the D-maltose derivative, were determined by X-ray crystallography of the diazido or dibromo precursors. While glycosidation of peracetylated galactopyranose with 1,3-dibromo-2-propanol in the presence of boron trifluoride afforded both anomers, the neighboring group participation of the 2-acetoxy group yielded a single anomer for the other substrates. This method has been used to synthesize a library of sugar-pendant diamines including an OH-protected derivative (6), and an N,N'-diisopropyl-substituted derivative (7). A similar series of reactions using 2,3-dibromo-1-propanol gave ethylenediamine-type derivatives (11), and bis(bromomethyl)bis(hydroxymethyl)methane (12) gave bisglucose-pendant derivatives (16).
Mikata
Y
Y
Department of Chemistry, Faculty of Science, Nara Women's University, Nara 630-8506, Japan.
Shinohara
Y
Y
Yoneda
K
K
Nakamura
Y
Y
Esaki
K
K
Tanahashi
M
M
Brudziñska
I
I
Hirohara
S
S
Yokoyama
M
M
Mogami
K
K
Tanase
T
T
Kitayama
T
T
Takashiba
K
K
Nabeshima
K
K
Takagi
R
R
Takatani
M
M
Okamoto
T
T
Kinoshita
I
I
Doe
M
M
Hamazawa
A
A
Morita
M
M
Nishida
F
F
Sakakibara
T
T
Orvig
C
C
Yano
S
S
D002240:Carbohydrate Sequence; D003959:Diamines / Q000138:chemical synthesis*; D007202:Indicators and Reagents; D008968:Molecular Conformation; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000138:chemical synthesis*; D014961:X-Ray Diffraction
D003959:Diamines; D007202:Indicators and Reagents; D009844:Oligosaccharides