Synthesis of Biologically Active Oligosaccharide Using Anomerization Reaction via Endocyclic Cleavage Reaction

2015 Fiscal Year Final Research Report

• Project/Area Number: 24590041
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Institute of Physical and Chemical Research
• Principal Investigator: Manabe Shino 国立研究開発法人理化学研究所, 伊藤細胞制御化学研究室, 専任研究員 (60300901)
• Project Period (FY): 2012-04-01 – 2016-03-31
• Keywords: 糖 / ピラノシド / 異性化 / エンド開裂反応 / 1,2-cis アミノグリコシド / 置換基効果

Outline of Final Research Achievements

The bond between anomeric position and external oxygen is cleaved in endocyclic cleavage reaction. Endocyclic cleavage reaction is rare in glycoscience. We found endocyclic cleavage reaction is promoted by protection of amino group at 2-amino group and 3-hydroxy group by cyclic carbamate group. Clear evidence of endocyclic cleavage reaction was demonstrated by capturing acyclic cation by reduction and intramolecular Friedel-Crafts reaction. Investigation on substituent effect reveals Ac group makes complete anomerization in various substrates. By using endocyclic cleavage reaction, existing multiple stereochemistries at anomeric position can be changed to α-isomer, which is difficult to be created by conventional glycosylation reaction. Novel α-linked chitosan oligomer was synthesized from β-chitosan in one-step.

Free Research Field

有機化学、糖質科学