From Higher Carbon Sugars to Carbocyclic Sugar Mimics

The convenient route (showing a historical background of the co-operation between the author and late Professor Aleksander Zamojski) to carbocyclic sugar mimics: derivatives of highly oxygenated bicyclo[4.3.0]nonanes and bicyclo[ 4.4.0]decanes from sugar chirons is presented. First, the paper describes the stereoselective synthesis of higher carbon sugars (up to 21 carbon atoms in the chain) starting from various simple derivatives of carbohydrates such as: sugar phosphoranes and phosphonates, sugar acetylenes, and finally sugar allyltins. The latter turned to be convenient starting materials for the preparation of highly versatile dienoaldehydes, via a controlled fragmentation with elimination of the stannyl moiety. These dienes were used for the stereoselective synthesis of highly oxygenated carbo-bicyclic derivatives.