Y Mikata; Y Shinohara; K Yoneda; Y Nakamura; K Esaki; M Tanahashi; Brudzinska, I; S Hirohara; M Yokoyama; K Mogami; T Tanase; T Kitayama; K Takashiba; K Nabeshima; R Takagi; M Takatani; T Okamoto; Kinoshita, I; M Doe; A Hamazawa; M Morita; F Nishida; T Sakakibara; C Orvig; S Yano
JOURNAL OF ORGANIC CHEMISTRY AMER CHEMICAL SOC 66 (11) 3783 - 3789 0022-3263 2001/06
[Refereed] 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).