Trineopentylphosphine: A Conformationally Flexible Ligand for the Coupling of Sterically Demanding Substrates in the Buchwald–Hartwig Amination and Suzuki–Miyaura Reaction

Trineopentylphosphine (TNpP) in combination with palladium provides a highly effective catalyst for the Buchwald–Hartwig coupling of sterically demanding aryl bromides and chlorides with sterically hindered aniline derivatives. Excellent yields are obtained even when both substrates include 2,6-diisopropyl substituents. Notably, the reaction rate is inversely related to the steric demand of the substrates. X-ray crystallographic structures of Pd­(TNpP)₂, [Pd­(4-<i>t</i>-Bu-C₆H₄)­(TNpP)­(μ-Br)]₂, and [Pd­(2-Me-C₆H₄)­(TNpP)­(μ-Br)]₂ are reported. These structures suggest that the conformational flexibility of the TNpP ligand plays a key role in allowing the catalyst to couple hindered substrates. The Pd/TNpP system also shows good activity for the Suzuki coupling of hindered aryl bromides