Palladiumcatalyzed annulation钯催化的环.pptVIP

Summary .Introduction . Annulation with 1,3-Diene, 1,2-Diene,Unsatured cyclopropanes and cyclobutanes, cyclic and bicyclic alkenes, Alkynes . Conclusion Introduction Palladium has been proved extraordinarily useful for the synthesis of a wide variety of heterocycles and carbocycles. Prior to 1990, there were a number of reports of the palladium-catalyzed synthesis of heterocycles by appending a heteroatom-containing unit onto existing functionality (heteroannulation) Few of those processes were very general in scope. Introduction Richard C. Larock, Department of Chemistry, Iowa State University From 1980’s to 2002 The palladium-catalyzed annulation of cyclic and bicyclic alkenes, unsaturated cyclopropanes and cyclobutanes, allenes, 1,3-and 1,4-dienes, as well as internal alkynes, by appropriately-substituted aryl or vinylic halides and triflates provides a very efficient, yet versatile route to a wide variety of heterocycles and carbocycles. Previous methods for annulation Annulation by Palladium Catalyst Application on Liquid Crystal Synthesis Offered various annulation routes for synthesizing discotic and calamatic liquid crystal molecules. Reaction with 1,3-Dienes Mechanism Reduction of the palladium(II) salt to Pd(0) Oxidative addition of the aryl halide to Pd(0)--- Rate determining step Arylpalladation of the carbon–carbon double bond to initially produce a σ-allylpalladium intermediate, which rapidly rearranges to the more Stable π-allylpalladium intermediate, Nucleophilic displacement of palladium by the internal nucleophile General Conditions The nature of the Pd catalyst don’t have a major effect on the annulation. Pd(OAc)2 readily available,preferable Pd(DBA)2 (DBA=dibenzylideneacetone) Pd(PPh3)4 Polar solvents N,N-dimethylformamide 1,3-Diene has to be excess, because it’s volatile Temperature 80-120°C Rate determining step oxidative addition