Starting from D-glucose, D-fructose and L-sorbose several m-oxa-n-thiabicyclics were synthesised. The different types of bicyclic compounds were in the chart.

Starting from glucose, several compounds were obtained. It was possible to introduce azide after as well as before the cyclisation step. The reaction of a bicyclic starting compound with azide was accompanied by an anomerisation. (Typ 1,2,5, and 6 were obtained from glucose)

Methyl-fructofuranosides, when used as starting material, formed bicyclic compounds typ 4,8 and9.

Starting from L-sorbose, bicyclic compounds with pyranoside (typ1 and 2) or furanoside (typ 3,7, and 8) structures could be obtained.

The thio-Mitsunobu reaction successfully lead to the desired thio-acatates when aldohexopyranosides derivatives from glucose as well as ketofuranosides derivatives from fructose or sorbose were used as starting compounds. The reaction preferentially took place at the primary hydroxy group.

If the thio-Mitsunobu reaction failed, the insertation of sulfur was achieved by nucleophilic attack of potassium thioacetate on a suitable substrate e.g. a mesylate or an epoxide.

A pdf you will find in Dateien.