Research On The Construction Of 1-indanone Compounds Based On Domino Reaction

As an important class of cyclic compounds,1-indanones have been found in many natural products and biologically active molecules.They are also frequently employed as building blocks in functional materials and pharmaceuticals.The intramolecular cyclization reactions,such as Nazarov cyelization of aryl vinyl ketones and the intramolecular Friedel-Crafts acylation of the 3-aryl aromatic acids or corresponding acyl chlorides,are common methods to generate 1-indanones.Alternatively,the intramolecular hydroacylation of alkenes,the oxidative cyclizations of cis-3-en-1-ynes,or the isomerization of ?-arylpropargyl alochols also afford 1-indanone motif.However,the prefunctionalized substrates and/or superstoichiometric Lewis acids are often required in these transformations,which limit their synthetic utility.Therefore,developing more concise methods for the synthesis of the diverse 1-indanone skeleton from commercially available starting materials has been an intense topic.Recently,transition-metal-catalyzed domino cyclization reactions based on C-H activation,which enable the formation of several bonds in one pot by using a single catalyst,have emerged as a promising tool to construct complex skeletons,because it may not only significantly simplify and shorten the synthetic route but also allow the use of readily available substrates.Aromatic acids have been widely used as attractive candidates in tandem cyclization reactions due to their wide availability and high reactivity.Compared with other guide groups,carboxyl groups,as a promising non-marking guide group,not only have the advantages of low cost,easy availability,variety,stability,and easy storage,but also have high reactivity and can convert to other functional groups.Based on the domino reaction of C-H activation directed by carboxyl,this thesis mainly focuses on the following three aspects of work.In the first chapter,the recent methods toward the synthesis of 1-indanones and 1-indanone spirocyclic compounds are reviewed.In the second chapter,1-indanones were synthesized via domino tandem cyclization reactions using aromatic acids and ?,?-unsaturated ketones as starting materials,[RuCl2(p-cymene)]2 as catalyst,MnCO3 as additive.A trace amount of water can promote the formation of 1-indanones.The tandem cyclization involves one-pot sequential reactions of C-H activation,conjugate addition,Dieckmann condensation,Michael addition,hydrolysis,which features commercially available starting materials,simple operations,the one-pot efficient construction of three C-C bonds and a broad substrate scope.It provides a simple and efficient reaction strategy for the synthesis of 1-indanone compounds with important biological activities.In the third chapter,spiroindanones were synthesized via domino tandem cyclization reactions employing aromatic acids and ?,?-unsaturated ketones as starting materials in the presence of[RuCl2(p-cymene)]2 and Mn(OAc)2.This process undergoes conjugate addition/intramolecular Dieckmann condensation/Michael addition reaction/intramolecular Aldol condensation reaction,which not only features commercially available starting materials,simple operations.Mn(?)plays a key role in the catalytic cycle.Especially,This reaction which constructs Four C-C bonds in one step exhibits high efficiency and broad substrate scope.In the last chapter,the innovation of this work was summarized.