Aminative Suzuki-Miyaura coupling

• 成果类型: Article
• 署名作者: Onnuch, Polpum; Ramagonolla, Kranthikumar; Liu, Richard Y.
• 署名单位: Harvard University
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-9813
• DOI: 10.1126/science.adl5359
• 发表日期: 2024-03-01
• 页码: 1019-1024
• 关键词: catalyzed trifluoromethylation; heteroaryl halides; allylic alcohols; substrate scope; boronic acids; aryl; efficient

摘要

The Suzuki-Miyaura and Buchwald-Hartwig coupling reactions are widely used to form carbon-carbon (C-C) and carbon-nitrogen (C-N) bonds, respectively. We report the incorporation of a formal nitrene insertion process into the Suzuki-Miyaura reaction, altering the products from C-C-linked biaryls to C-N-C-linked diaryl amines and thereby joining the Suzuki-Miyaura and Buchwald-Hartwig coupling pathways to the same starting-material classes. A combination of a bulky ancillary phosphine ligand on palladium and a commercially available amination reagent enables efficient reactivity across aryl halides and pseudohalides, boronic acids and esters, and many functional groups and heterocycles. Mechanistic insights reveal flexibility on the order of bond-forming events, suggesting potential for expansion of the aminative cross-coupling concept to encompass diverse nucleophiles and electrophiles as well as four-component variants.