Regioselective Orthopalladation of (Z)-2-Aryl-4-Arylidene-5(4H)-Oxazolones: Scope, Kinetico-Mechanistic, and Density Functional Theory Studies of the C鈥揌 Bond Activation

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• 作者：Gheorghe-Doru Roiban ; Elena Serrano ; Tatiana Soler ; Gabriel Aullo虂n ; Ion Grosu ; Carlos Cativiela ; Manuel Marti虂nez ; Esteban P. Urriolabeitia
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：September 5, 2011
• 年：2011
• 卷：50
• 期：17
• 页码：8132-8143
• 全文大小：1176K
• 年卷期：v.50,no.17(September 5, 2011)
• ISSN：1520-510X

文摘

Orthopalladated complexes derived from (Z)-2-aryl-4-arylidene-5(4H)-oxazolones have been prepared by reaction of the oxazolone with palladium acetate in acidic medium. The reaction is regioselective, only the ortho C鈥揌 bond of the arylidene ring being activated, producing a six-membered ring. The scope and reaction conditions of the orthopalladation are dependent on the acidity of the solvent. In CF₃CO₂H a large number of oxazolones can be metalated under mild conditions. As acidity decreases a lesser number of oxazolones can be efficiently palladated and harsher conditions must be used to achieve similar yields. The C鈥揌 bond activation in acidic medium agrees with an ambiphilic mechanism, as determined from kinetic measurements at variable temperature and pressure for different oxazolones substituted at the arylidene ring. The mechanism has been confirmed by density functional theory (DFT) calculations, where the formation of the six-membered ring is shown to be favored from both a kinetic and a thermodynamic perspective. In addition, the dependence of the reaction rate on the acidity of the medium has also been accounted for via a fine-tuning between the C鈥揌 agostic precoordination and the proton abstraction reaction in the overall process occurring on coordinatively saturated [Pd(魏^N-oxazolone)(RCO₂H)₃]²⁺.