Abstract
The syntheses of new types of vinyl sugars are described whose vinyl groups are connected with the monosaccharide by a CC bond. Such monomers can be polymerized by radical as well as by anionic initiation. Starting from D‐mannitol, D‐gluconolactone, D‐galactose, and D‐fructose, the isopropylidene‐protected aldehydes (R)‐2,3‐isopropylidene‐D‐glyceraldehyde (3), 2,3;4,5‐di‐O‐isopropylidene‐aldehydo‐D‐arabinose (4), 1,2;3,4‐di‐O‐isopropylidene‐α‐D‐galacto‐hexodialdo‐1,5‐pyranose (5), and 2,3;4,5‐di‐O‐isopropylidene‐β‐D‐arabino‐hexosulo‐2,6‐pyranose (6) were prepared. Grignard reaction of the aldehyde compounds with 4‐vinylphenylmagnesium chloride in tetrahydrofuran (THF) yielded the new styryl monomers of type 1, in each case as a mixture of two diastereoisomers. The corresponding reaction with vinylmagnesium bromide furnished a mixture of two diastereoisomeric allyl alcohol derivatives. Subsequent Swern oxidation (DMSO/(COCl)~2~) gave the vinyl ketones of type 2. A scale‐up procedure (20 L flask) allowed eight different monomers to be prepared on a 50–200 g scale. Furthermore, the synthesis of the 2,3;4,5‐di‐O‐isopropylidene‐β‐D‐fructopyranose could be considerably improved.