Stereospecific synthesis of eight-membered polyhydroxy carbocycles via TIBAL-promoted Claisen rearrangement

The stereoselective synthesis of novel eight-membered polyhydroxy carbocycles was achieved from D-glucose via mercuriocyclization and triisobutylaluminum (TIBAL)-promoted Claisen rearrangement. Along with rearrangement, TIBAL also promoted debenzylation and cycloaddition, and a 3,9-dioxa-bicyclo[3.3.1]nonane derivative was formed. The stereoselectivity of mercuriocyclization was attributed to the interaction between mecurio and vinyl moities. and this interaction also assisted the mercurio derivative to exist in an abnormal conformation. The configuration and/or conformation of intermediates and products were identified by NMR spectral analyses.Chemistry, OrganicSCI(E)0ARTICLE131985-198