Cheap Transition Metal Salts Catalyzed Study Of Forming And Capturing O-QDM

Discovered in1928, the Diels-Alder reaction played a huge role and advantage inOrganic synthetic chemistry, especially in the synthesis of natural macromolecular compoundduring the nearly hundred years.Diels-Alder reaction which have the advantages of high atom economy, high stereo-selectivity, predicted results could be predicted was being the best method of structuringsix-member ring. o-QDM which is widely used in Diels-Alder reaction as special cis-diene isa sort of highly unstable activated intermediate and used in structuring benz-six-member ring.The thesis can be summarized as the following two parts:Part One: the Diels-Alder Reaction of Forming o-QDM Catalyzed by Transition MetalSaltsA methodology for stereoselective synthesis of polysubstituted tetrahydronaphtholscatalyzed by [Ag+]/NPO has been developed by our team. Inspired by this discovery,benzannulation reaction between2-(2-oxoethyl) arylaldehydes and had been studiedsystematically in chapter two of this work. Catalyzed by transition metal salts, o-QDMintermediate was formed in site through reactant2-(2-oxoethyl) arylaldehydes by enolization.Then, o-QDM intermediate was captured by alkynes immediately and naphthalene derivativeswere produced. Condition of this reaction is warm and mild with wide substrate scope andhigh atom economy. Especially, FeCl3as the catalyst made the reaction more economic、environment friendly and practical.Part Two: Cascade Diels-Alder Reaction Catalyzed by Transition Metal SaltsThis part which replaced expensive and rare gold catalyst to cheap transition metal saltscarried out cascade Diels-Alder reaction between o-alkynylbenzaldehyde and norbornene.Through a large number of test, the optimal reaction conditions that is20mol%ZnI2in DCEat80oC for12h were obtained.