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 C-C 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-alpha-D-galacto-hexodialdo-1,5-pyranose (5), and 2,3;4,5-di-O-isopropylidene-beta-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-beta-D-fructopyranose could be considerably improved.