The Intermolecular Pauson—Khand Reaction of Sugar-Derived Azaenynes: A Case of Total Diastereoselectivity.

Sugar azaenynes 1a and 1b, easily available from D‐glucal and D‐galactal, respectively, react with norbornene and norbornadiene under Pauson‐Khand conditions to give the intermolecular adducts as major or exclusive product. In all cases only one diastereomer was obtained in convenient yield. This reaction constitutes an unprecedented case of totally diastereoselective intermolecular Pauson‐Khand reaction using a sugar moiety as chiral auxiliary.