Glycals in Organic Synthesis: The Evolution of Comprehensive Strategies for the Assembly of Oligosaccharides and Glycoconjugates of Biological Consequence

Wiley - Tập 35 Số 13-14 - Trang 1380-1419 - 1996
Samuel J. Danishefsky1, Mark T. Bilodeau1
1Laboratory for Bioorganic Chemistry The Sloan-Kettering Institute for Cancer Research 1275 York Avenue, Box 106, New York, NY 10021 (USA)

Tóm tắt

Abstract

This review provides a personal account of the explorations of a research group in oligosaccharide and glycoconjugate construction. The journey began twenty years ago with the study of Diels–Alder reactions of complex dienes. By extending this methodology to aldehydo‐type heterodienophile equivalents, access to unnatural glycals was gained (LACDAC reaction). From this point a broad‐ranging investigation of the use of glycals in the synthesis of oligosaccharides and other glycoconjugates was begun. Mobilization of glycals both as glycosyl donors and glycosyl acceptors led to the strategy of glycal assembly. Several new glycosylation techniques were developed to provide practical underpinning for this logic of glycal assembly. Glycal‐based paradigms have been shown to be nicely adaptable to solid phase supported synthesis. Moreover, glycal assembly—both in solution and on solid phases—has been used to gain relatively concise and efficient entry to a variety of biologically interesting and potentially valuable constructs. Some of these syntheses, particularly in the field of tumor antigens, have led to novel compounds which are in the final stages of preclinical assessment. This review presents an account of the chemical reasoning at the center of the program.

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