A Highly Active Catalyst for Pd-Catalyzed Amination Reactions: Cross-Coupling Reactions Using Aryl Mesylates and the Highly Selective Monoarylation of Primary Amines Using Aryl Chlorides

• Published in: Journal of the American Chemical Society Vol. 130; no. 41; pp. 13552 - 13554
• Main Authors: Fors, Brett P, Watson, Donald A, Biscoe, Mark R, Buchwald, Stephen L
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 15.10.2008; Amer Chemical Soc
• Subjects: Amination; Amines - chemistry; Amines - classification; Catalysis; Chemistry; Chemistry, Multidisciplinary; Chlorine Compounds - chemistry; Cross-Linking Reagents - chemistry; Crystallography, X-Ray; Ligands; Magnetic Resonance Spectroscopy; Mesylates - chemistry; Models, Molecular; Molecular Structure; Palladium - chemistry; Physical Sciences; Science & Technology; HETEROARYL; ROOM-TEMPERATURE; LIGANDS; C-N; PHOSPHINES; BOND-FORMING REACTIONS; COMPLEXES; LONG-LIVED CATALYSTS; OXIDATIVE ADDITION; TOSYLATES
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja8055358

A catalyst system based on a new biarylmonophosphine ligand (BrettPhos) that shows excellent reactivity for C−N cross-coupling reactions is reported. This catalyst system enables the use of aryl mesylates as a coupling partner in C−N bond-forming reactions. Additionally, the use of BrettPhos permits the highly selective monoarylation of an array of primary aliphatic amines and anilines at low catalyst loadings and with fast reaction times, including the first monoarylation of methylamine. Lastly, oxidative addition complexes of BrettPhos are included, which provide insight into the origin of reactivity for this system.