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Chemodivergent Palladium‐Catalyzed Processes: Role of Versatile Ligands
Author(s) -
Nava Paola,
Clavier Hervé,
Gimbert Yves,
Giordano Laurent,
Buono Gérard,
Humbel Stéphane
Publication year - 2015
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201500809
Subject(s) - palladium , catalysis , chemistry , cycloaddition , interchangeability , combinatorial chemistry , organic chemistry , computer science , programming language
Whereas the reaction of norbornadiene with terminal alkynes in the presence of a phosphapalladacycle catalyst leads to the formation of hydroalkynation products, the use of phosphinous acid–phosphinito‐containing palladium complexes gives rise to formal [2+1] cycloadducts. An experimental and computational approach was employed to study the mechanisms of the palladium‐promoted hydroalkynation and [2+1] cycloaddition. On the one hand, experiments highlight the crucial role of acidolysis steps on the catalytic activities. On the other hand, DFT calculations demonstrate the specificity of the phosphinito–phosphinous acid ligands, that is, the non‐equivalence of the two phosphorus atoms but the interchangeability of their properties. These results may have important implications for the mechanism of other palladium‐catalyzed transformations especially those involving phosphapalladacycles and phosphinous acid–phosphinito‐containing palladium complexes.