Highly Diastereo‐ and Enantioselective Pd‐Catalyzed Spiroaminoalkylation: One‐Step Construction of Multifunctional Angular Polycyclic Amines

Abstract Angular polycycles are ubiquitous in natural products with significant biological properties. However, the straightforward catalytic asymmetric synthesis of spirocyclic scaffolds with multiple stereogenic centers from readily available starting materials remains largely underdeveloped and a formidable challenge. Using the aminoalkyl cyclopalladated complex as the key intermediate, we report herein the first example of diastereo‐ and enantioselective multifunctional angular tetracyclic‐ and pentacyclic amines synthesis through palladium‐catalyzed spiroaminoalkylation/allylic substitution reaction (up to 92% yield, up to 99% ee). The synthetic versatility of this methodology is underscored by the efficient synthesis of chiral phosphine ligands, which further demonstrates its robust utility in concisely constructing versatile chiral ligands.