Selective Monoarylation of Primary Amines Using the Pd‐PEPPSI‐IPent^Cl Precatalyst

Abstract

A single set of reaction conditions for the palladium-catalyzed amination of a wide variety of (hetero)aryl halides using primary alkyl amines has been developed. By combining the exceptionally high reactivity of the Pd-PEPPSI-IPent(Cl) catalyst (PEPPSI=pyridine enhanced precatalyst preparation, stabilization, and initiation) with the soluble and nonaggressive sodium salt of BHT (BHT=2,6-di-tert-butyl-hydroxytoluene), both six- and five-membered (hetero)aryl halides undergo efficient and selective amination.

Well-defined nickel and palladium precatalysts for cross-coupling

“…Recent work from the groups of Nolan and Organ has demonstrated that the PEPPSI scaffold can accommodate bulky ligands, such as IPr* (REF. 49), IPent (REFS 50–52), IPent Cl (REFS 53–56) and IHept Cl (REFS 57,58), without any need to modify the precatalyst structure. Use of the PEPPSI framework with these newly designed NHC ligands has led to increased reactivity for the arylation of amines (using IPr* (REF.…”

“…Use of the PEPPSI framework with these newly designed NHC ligands has led to increased reactivity for the arylation of amines (using IPr* (REF. 49) and IPent Cl (REFS 55,56)), as well as highly selective Negishi couplings with secondary alkylzinc reagents (using IPent Cl (REF. 53) and IHept Cl (REFS 57,58)).…”

Suzuki–Miyaura and Hiyama coupling catalyzed by PEPPSI-type complexes with non-bulky NHC ligand

“…Air and moisture stable PEPPSI complexes have found many applications as catalysts of C C and C N cross-coupling reactions due to their ready activation under the reaction conditions [3][4][5][6][7] . In addition, PEPPSI complexes can be easily obtained and are easy to handle in contrast to other Pd-NHC precursors [8][9][10][11][12][13][14][15].…”

Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ‐H)2Os3(CO)10]

“…Amination of the vinyl chloride ligand gives rise to [(µ‐H)Os 3 (µ‐CH=CHNR 2 )(CO) 10 ] ( 2′ ). Such reactions usually require a catalyst and, as a rule, high temperatures , . In our case, the activation of vinyl chloride is due to the σ,π‐coordination of two osmium atoms.…”