The preparation of new types of polymerizable vinyl sugars with CC bonds between sugar and double bond

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.