Sugar-pendant diamines.

Y Mikata, Y Shinohara, K Yoneda, Y Nakamura, K Esaki, M Tanahashi, I Brudziñska, S Hirohara, M Yokoyama, K Mogami, T Tanase, T Kitayama, K Takashiba, K Nabeshima, R Takagi, M Takatani, T Okamoto, I Kinoshita, M Doe, A Hamazawa, M Morita, F Nishida, T Sakakibara, C Orvig, S Yano

Index: J. Org. Chem. 66(11) , 3783-9, (2001)

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Abstract

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).