Study On Au(I) Catalyzed Vinylogous Conia Ene Reaction

In this paper,we mainly studied the Au(I)-catalyzed vinylogous Conia ene reaction including the optimization of reaction conditions,its tolerable substrates scope and its application in the total synthesis of natural product ganocin B.The thesis is divided into three chapters.Chapter 1: Research progress of intramolecular Conia ene reactions involving alkynesConia ene reaction is an olefinization(or alkylation)reaction occurred at the αposition of a carbonyl group.Based on its reaction mechanism,Conia ene reaction is a coupling transformation between enols and alkynes(or alkenes).As an important carbon-carbon bond formation reaction,it is widely used in the construction of complex ring systems.In this chapter,we first briefly introduced the discovery of Conia ene reaction and its common activation models.Then the research progress of Conia ene reaction in past 20 years are discussed in detail based on different activation models.And finally we summarized the recent application of Conia ene reaction in the total synthesis of natural products in.Chapter 2: The Conia ene reaction catalyzed by Au(I)was used to construct the all-carbon [6.5] spirocyclic skeletons structureVinylogous Conia ene reaction is developed on the basis of Conia ene reaction and vinylogous principle.In this chapter,we mainly studied the construction of densily functionalized [6.5] spiro compounds via an Au(I)-catalyzed vinylogous Conia ene reaction.We used a conjugated cyclohexenone with an alkynyl side chain at its γposition as the model substrate.Firstly,we screened to find the optimized reaction conditions.And then we explored the tolerable substrate scopes of this vinylogous Conia ene reaction under the optimized conditions.Finally,we tried to use this reaction as a key conversion step to realize the chemical total synthesis of natural ganocin B.Chapter 3: The Conia ene reaction was used to construct spiral ring compounds containing butenolactone structureIn this chapter,we mainly studied the construction of [5.5] spirocyclic compounds containing a butyrolactone motif through a designed vinylogous Conia ene reaction.We have screened various conditions and have not found the suitable reaction conditions to realize this transformation.In the future,we will realize this transformation by introducing another new activating group on the substrate.