ABSTRACT
The extensive development of palladium chemistry over the last two decades has impacted on the field of C-glycoside synthesis. This chapter covers the chemistry of p-allyl complexes and how this type of chemistry has been successfully applied to C-glycoside formation. It addresses the use of Heck type couplings in anomeric carbon-carbon bond formation. Engelbrecht and Holzapfel improved this type of reaction by employing pseudoglycals that have a carbonate group at the anomeric position. The carbon-carbon bond that is formed occurs between C-1 of the enol ether and the incoming carbon group with syn addition of the palladium complex. The nature of the elimination step of palladium from the product can be controlled to afford enol acetates or olefinic C-glycosides. The chapter concentrates on the use of the Stille coupling to make C-1 substituted glycals that are amenable to further transformation.
