A furanose‐derived 2,3‐anhydro‐exo‐glycal, readily available from D‐mannose in four steps, has proven to be a useful substrate in the preparation of a variety of highly functionalized C‐1 glycals. Upon treatment with Pd0 it affords a π‐allyl palladium complex that can react with nucleophiles such as amines, ethyl malonate, or vinylstannanes. On the other hand, umpolung of the π‐allyl palladium complex with Et2Zn facilitates its reaction with electrophilic aldehydes and ketones.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)