Hydrofunctionalization of Polyunsaturated Hydrocarbons via Palladium(0) π‐Lewis Base‐Mediated Protonation

作者：Meng‐Qi Gan, Wei Du, Ying‐Chun Chen · 发表于：ChemCatChem · 年份：2025 · DOI：10.1002/cctc.202501167 · 被引用次数：5 · 研究领域：Synthesis of Indole Derivatives、Chemical Synthesis and Reactions、Asymmetric Synthesis and Catalysis

Abstract Palladium(0)‐catalyzed asymmetric hydrofunctionalization of polyunsaturated hydrocarbons offers an atom‐economic and highly stereoselective strategy for the synthesis of chiral molecules. Traditionally, these transformations are initiated via well‐established mechanisms such as Pd─H insertion or ligand‐to‐ligand hydrogen transfer (LLHT). More recently, a distinct catalytic mode has emerged, wherein Pd 0 acts as a π‐Lewis base catalyst to promote the outer‐sphere protonation of diverse polyunsaturated hydrocarbons, such as 1,3‐dienes, 1,3‐enynes, and allenes, through η 2 ‐coordination and subsequent π‐backdonation, emphasizing its unique mechanistic features and reaction patterns. Importantly, this approach has enabled the construction of a broad array of C─C, C─N, C─O, and C─P bonds with the resultant Pd II intermediates, generally in an enantioselective manner, offering efficient synthetic routes to chiral scaffolds and paving new avenues for asymmetric hydrofunctionalization.