Chiral and stereoselective total synthesis of novel immunosuppressant FR65814 from D-glucose

The chiral synthesis of the immunosuppressive sesquiterpene; FR65814 1 is d escribed. The cyclohexane ring in 1 was prepared in an optically active for m from D-glucose using Ferrier's carbocyclization reaction, and the carbon side-chain in 1 was stereoselectively introduced via chirality transfer by way of Claisen rearrangement of the cyclohexenol derivative, followed by Pd -catalyzed Stilie coupling. The bis-epoxide function was stereoselectively constructed by sulfur ylide chemistry and vanadium catalyzed epoxidation of a homoallyl alcohol derivative. This first total synthesis fully confirmed the proposed absolute structure of FR65814. (C) 1999 Elsevier Science Ltd. All rights reserved.