Palladium-cataivzed1,6-Envnes Dehvdroaromatization To Construct Isoindolinone And Fluorenol Skeleton By Means Of Domino Reactions

Palladium-catalyzed domino reaction has been highlighted as one ofthe research frontier，which has been widely used for the construction offusedcycles, in the total synthseis of natural products and incombinatorial chemistry. Recently，more and more domino reactions havebeen utilized for the efficient and stereoselective construction of complexmolecules from simple precursors in a single process，and have quicklybecome a powerful and efficient tool in organic chemistry. In this thesis，we have developed a palladium-catalyzed dehydroaromatization dominomethod to construct isoindolinone and fluorenol skeleton. The startingmaterials have been maximized to convert into the desired compounds，avoiding energy-costing processes that involve multi-step syntheses. So,these reactions have featured with low-carbon green chemistry, whichoffer a valuable addendum to methodology for the synthesis offusedcyeles. The discussions and results are listed as following:1. In this work, we have developed a novel tandem palladiumcatalyzed including an N-bearing1,6-enynes to the corresponding twelvefused benzoisoindol-ones in good yield through C-C coupling, C-Hactivation and intramolecular dehydroaromatization, in the presence ofPd（OAc）2/PPh3catalyst system and DMF/H₂O （V/V=5:1） as sovlent at130°C. In the same conditions, we have also tested some typical substrates with ethyl4-bromobenzoate and3-bromoquinoline, and theexciting result is that we obtain five benzoisoindolones and threephenanthridin derivatives in moderate yield.2. In this paper, we developed a novel domino method and hydrogentransfer reaction for the synthesis of twenty-six fused benzo[b]fluorenolcompounds through intramolecular dehydroaromatization and carbonylreduction, leading to a secondary alcohol by the treatment of the linearen-yn-ones with3-bromoprop-1-yne catalyzed by palladium compounds.We tested some different substrates, explored electronic and space effecton this reaction and proposed probable mechanism. The readilyaccessible starting materials, fused benzofluorenols showing a broadrange of biological and pharmaceutical activity make the reaction highlyvaluable in the medicinal development.All the products were well characterized by1^H NMR,13^C NMR, IRand HRMS. The relative configurations of some typical products wereconfirmed by X-ray crystallographic analysis.