From Exocyclic-Olefinic Carbohydrate Derivatives to Functionalized Carbocyclic Compounds

Abstract

As the structural constituents of many naturally occurring molecules, synthesis of functionalized carbocyclic derivatives has been widely investigated. Among numerous approaches to construct carbocyclic compounds, there is an efficient way of forming carbocyclic derivatives by the use of various monosaccharides as chiral building blocks. In this review, synthetic conversions to functionalized carbocyclic compounds from exocyclic-olefinic saccharides and their applications to synthesis of some natural products or natural product-like analogues will be discussed. The emphases will be put on the latest methodology developments of ring-conversion rearrangement reactions catalyzed by metal catalysts.

Synthesis of monoglycosides, bisglycosides and open-chain ketoacetals from sugar derived exocyclic enol ethers

“…7 Several synthetic reports for these vinyl ethers via dehydrohalogenation of 5-halogeno-furanose derivatives, 8 Bamford-Stevens rearrangement of 5-tosylhydrazono-furanose derivatives 9 and Wittig reaction of aldehydes with sugar-based triphenylphosphonium salts 10 have been reported in the literature. Attempts to elaborate the synthetic utility of these ethers in producing glycosides, 11 polyethers, 12 spiroketals 13 and related compounds 14 including heterocycles, 15 carbocyles, 16 and nucleosides 17 using coupling reactions, 18 radical processes 19 and cycloaddition reactions 20 have generated molecules of diverse nature. Nevertheless, the chemistry of these systems is less developed as compared to endocyclic vinyl ethers that allow regio-and stereoselective transformation, glycosylation as well as C-C and C-heteroatom bond formations at the anomeric centre.…”