Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

作者：Wenbo Li, Junliang Zhang · 发表于：Accounts of Chemical Research · 年份：2024 · DOI：10.1021/acs.accounts.3c00648 · 被引用次数：49 · 研究领域：Catalytic C–H Functionalization Methods、Asymmetric Hydrogenation and Catalysis、Catalytic Cross-Coupling Reactions

Conspectus Palladium catalysis, as one of the most important strategies in asymmetric synthesis, has continuously attracted the attention of organic chemists. With the development of chiral ligands, increasingly challenging reactions and substantial progress in asymmetric catalysis are being realized. Since 2014, we have focused on exploiting a series of sulfinamide phosphine ligands called “Sadphos,” including Ming-Phos, Xu-Phos, Xiao-Phos, Xiang-Phos, TY-Phos, PC-Phos, GF-Phos, and WJ-Phos. These ligands can be easily prepared in two to four steps using commercial materials. These new types of ligands have shown remarkable performance in transition-metal-catalyzed reactions, especially in Pd-catalyzed transformations. X-ray diffraction analysis, mechanistic studies, and density functional theory calculations have revealed that Sadphos ligands can coordinate with the Pd 0 and Pd II species in the Pd 0 /P, Pd 0 /P,S, or Pd II /P,O modes. This Account summarizes our recent efforts toward palladium-catalyzed enantioselective reactions using Sadphos ligands. These ligands were found to be privileged and very crucial to promote the reactions by increasing the reactivity and enantioselectivity. Ming-Phos is an effective ligand in Pd-catalyzed asymmetric coupling and intramolecular Heck reactions, providing highly enantioselective trisubstituted allenes, axially chiral anilides, gem -diarylmethine silanes, and disubstituted dihydroisoquinolinones. Incorporation of an electron-rich ...