Design, Synthesis, and Application of Chiral C2‐Symmetric Spiroketal‐Containing Ligands in Transition‐Metal Catalysis

Abstract

We present an expedient and economical route to a new spiroketal‐based C2‐symmetric chiral scaffold, termed SPIROL. Based on this spirocyclic scaffold, several chiral ligands were generated. These ligands were successfully employed in an array of stereoselective transformations, including in iridium‐catalyzed hydroarylations (up to 95 % ee), palladium‐catalyzed allylic alkylations (up to 97 % ee), intermolecular palladium‐catalyzed Heck couplings (up to 94 % ee), and rhodium‐catalyzed dehydroalanine hydrogenation (up to 93 % ee).The expedient synthesis of a C2‐symmetric spiroketal‐based chiral scaffold is reported, which was elaborated into several chiral ligands. These were employed in an array of stereoselective transformations, including iridium‐catalyzed hydroarylation, palladium‐catalyzed allylic alkylation, and rhodium‐catalyzed dehydroalanine hydrogenation.