2003 Fiscal Year Final Research Report Summary

Synthesis of chiral auxiliary and multi-activation ligand having phosphonylated sugar moiety and their application for asymmetric synthesis

Research Project

Project/Area Number	14550823
Research Category	Grant-in-Aid for Scientific Research (C)
Allocation Type	Single-year Grants
Section	一般
Research Field	Synthetic chemistry
Research Institution	Shinshu University
Principal Investigator	IWAO Yamamoto Shinshu University, Department of Functional Polymer Science, Professor, 繊維学部, 教授 (60021169)
Co-Investigator(Kenkyū-buntansha)	FUJIMOTO Tetsuya Shinshu University, Department of Functional Polymer Science, Associate Professor, 繊維学部, 助教授 (90209099)
Project Period (FY)	2002 – 2003
Keywords	chiral auxiliary / Diels-Alder reaction / phosphonylated sugar / asymmetric synthesis / phosphenium cation
Research Abstract	Reaction of methyl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside with two equivalents of diphenylphosphenium cation at 0° C gave the α-and β-1-phosphonylated 2-enopyranosides as major products. Similarly, Reaction of diphenylphosphenium cation with tri-O-acetylglycal afforded the same products in a similar ratio. By contrast, a reaction with tri-O-benzylglucal at reflux temperature of dichloromethane afforded the 3-phosphonylated sugar as a major product. These reactions would proceed via stable allyl cations. Furthermore, the 3-phosphonylated sugar was useful for chiral auxiliary. For example, Diels-Alder reaction of an acrylate ester of the 3-phosphonylated sugar with eyclopentadiene gave a cycloadduct in good yield with excellent diastereoselectiviry.

(2 results)