Synthesis of stereoregular heteropolysaccharides having amino-groups by ring-opening copolymerization of 1,6-anhydro-azido-sugar derivatives

✍ Scribed by Uryu, Toshiyuki ;Hatanaka, Kenichi ;Matsuzaki, Kei ;Kuzuhara, Hiroyoshi

• Book ID: 105334651
• Publisher: John Wiley and Sons
• Year: 1983
• Weight: 521 KB
• Volume: 21
• Category: Article
• ISSN: 0360-6376
• DOI: 10.1002/pol.1983.170210805

✦ Synopsis

Abstract

The cationic, ring‐opening copolymerization of 1,6‐anhydro‐2‐azido‐3,4‐di‐0‐benzyl‐2‐deoxy‐(2‐ABG), ‐3‐azido‐2,4‐di‐0‐benzyl‐3‐deoxy‐ (3‐ABG), ‐4‐azido‐2,3‐di‐0‐benzyl‐4‐deoxy‐β‐D‐glucopyranose (4‐ABG) with 1,6‐anhydro‐2,3,4‐tri‐0‐benzyl‐β‐D‐glucopyranose (LGTBE) was investigated with phosphorus pentafluoride as catalyst at low temperatures, giving highly stereoregular, (1→6)‐α‐linked copolymers with number‐average molecular weights of 3.90 × 10^4^−9.27 × 10^4^. Structure and composition of the copolymers were determined by ^1^H‐ and ^13^C‐NMR spectroscopies and elemental analysis, which indicated that copolymerization occurred in a stereoregular manner to give azido groups containing (1→6)‐α‐linked glucopyranan derivatives. The differences in polymerizability among the three azido monomers are discussed. Regioselective reduction of three kinds of heteropolysacharide derivatives which had different quantities of azido groups at C‐2, ‐3, or ‐4 position with lithium aluminum hydride and subsequent debenzylation of the copolymers with sodium in liquid ammonia produced amino‐group‐containing heteropolysaccharides.