A General Palladium–Phosphine Complex To Explore Aryl Tosylates in the N‐Arylation of Amines: Scope and Limitations. Issue 17 (28th June 2018)

• Record Type: Journal Article
• Authors: Choy, Pui Ying; Chung, Kin Ho; Yang, Qingjing; So, Chau Ming; Sun, Raymond Wai‐Yin; Kwong, Fuk Yee
• Is Part Of: Chemistry, an Asian journal. Volume 13:Issue 17(2018)
• Page Start: 2465
• Page End: 2474
• Publication Date: 2018-06-28
• Subjects: amination -- C−N bond formation -- cross-coupling -- palladium -- phosphanes; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201800575
• Languages: English
• ISSNs: 1861-4728

Abstract

Abstract: The scope and limitations of the monoselective N‐arylation of various amines by using aryl and hetaryl tosylates are presented. The air‐stable and easily accessible Pd(OAc)2 /CM‐phos {CM‐phos=2‐[2‐(dicyclohexylphosphino)phenyl]‐1‐methyl‐1 H ‐indole}catalyst system was able to deal with a wide range of aryl tosylate substrates as well as amine nucleophiles, including primary and secondary cyclic/acyclic aliphatic amines and anilines. NH‐Bearing heterocycles such as indole, carbazole, pyrrole, 10‐phenothiazine, and 10‐phenoxazine were shown to be feasible coupling partners under this catalytic system. The described reaction conditions tolerate a wide range of functional groups and allow an array of aromatic amines as well as unsymmetrical amine products to be easily accessed from the various phenolic derivatives. Interestingly, this catalyst system even offers the opportunity to perform the reaction in water medium. We also report the intermolecular coupling of optically active α‐central chiral amines with aryl tosylates without erosion of the enantiomeric purity. Abstract : Arylation sensation : A general method for the monoarylation of various amines by using aryl and hetaryl tosylates is developed. The air‐stable and easily accessible Pd(OAc)2 /CM‐phos system can be used with a wide range of aryl tosylates and amine nucleophiles, including primary and secondary cyclic/acyclic aliphatic amines and anilines. N‐Heterocycles are feasible coupling partners under the catalytic system.