Sugar-Pendant Diamines

• Published in: Journal of organic chemistry 2001-06, Vol.66 (11), p.3783-3789
• Main Authors: Mikata, Yuji, Shinohara, Yoshie, Yoneda, Kazumi, Nakamura, Yuka, Esaki, Kimiko, Tanahashi, Maki, Brudziñska, Izabela, Hirohara, Shiho, Yokoyama, Mika, Mogami, Kaoru, Tanase, Tomoaki, Kitayama, Takashi, Takashiba, Katsuki, Nabeshima, Kenji, Takagi, Rie, Takatani, Masahiko, Okamoto, Tadashi, Kinoshita, Isamu, Doe, Matsumi, Hamazawa, Akihisa, Morita, Masanori, Nishida, Fumiko, Sakakibara, Toru, Orvig, Chris, Yano, Shigenobu
• Format: Article
• Language: English
• Subjects: Carbohydrate Sequence; Diamines - chemical synthesis; Indicators and Reagents; Molecular Conformation; Molecular Sequence Data; Oligosaccharides - chemical synthesis; X-Ray Diffraction
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo001702+

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).