Mechanism of Acyl Group Migration in Carbohydrates

Abstract

Acyl group migration has been the subject of several studies. Such migration processes may cause problems during synthesis, isolation, and purification of different acyl-bearing compounds, and have biological relevance, for example, in the metabolism of pharmaceuticals. Considering the recent evidence of acyl group migration being possible even over glycosidic bonds, it could be hypothesized to be involved also in the regulation of biological activity of natural polysaccharides in the host cells. Migrations are mostly observed in carbohydrates, typically having several hydroxyl groups near each other. Several studies have investigated the migration in a single or only a few different carbohydrate molecules, providing different suggestions for the mechanisms of migration, seldom supported by comprehensive computational investigations. In this concept article we discuss the recent progress on the mechanistic aspects of acyl group migration, with carbohydrates in particular focus.

Versatile approach towards fully desymmetrized trehalose with a novel set of orthogonal protecting groups

“…Given the propensity of the acetyl protecting group to migrate under a variety of chemical conditions ( Lassfolk and Leino, 2023 ; Lassfolk and Leino, 2023 ), the orthogonally protected 2,2′- O -levulinoyl derivatives 17 and 23 were selected for the development of an advanced synthetic route. To pave the way for further desymmetrization, the TBDMS groups in 17 and 23 were removed, and the adjacent hydroxyl groups in 18 and 24 at C2´/C3´ and C2/C3, respectively, were protected as cyclic TIPDS ethers.…”