Chemodivergent Palladium‐Catalyzed Processes: Role of Versatile Ligands

摘要: Whereas the reaction of norbornadiene with terminal alkynes in presence a phosphapalladacycle catalyst leads to formation hydroalkynation products, use phosphinous acid–phosphinito-containing palladium complexes gives rise formal [2+1] cycloadducts. An experimental and computational approach was employed study mechanisms palladium-promoted cycloaddition. On one hand, experiments highlight crucial role acidolysis steps on catalytic activities. theother DFT calculations demonstrate specificity phosphinito–phosphinous acid ligands, that is, non-equivalence two phosphorus atoms but interchangeability their properties. These results may have important implications for mechanism other palladium-catalyzed transfor- mations especially those involving phosphapalladacycles