Studies On The Synthesis And Reactions Of P-quinols

p-Quinols,which bearing hydroxyl and carbonyl groups with a carbon-carbon double bond served as a Michael receptor,are useful synthons in organic synthesis.Previous studies have been limited to the use of the hydroxyl group and the ?-carbon atom of p-quinols mainly for the construction of hydrofuran rings to form hydrobenzofurans.Therefore,it's important to develop new reactions using multiple reaction sites of p-quinols to expand the application of p-quinols in organic synthesis and to rapidly construct various complex structures such as carbo-and heterocycles and bridging motifs.In recent years,our research group has been devoted to the applications of 4-trifluoromethylated p-quinols in organic synthesis,and has achieved a series of good results.For example,a variety of multi-substituted trifluoromethylated aromatic compounds were synthesized using 4-trifluoromethylated p-quinols as the aromatic precursors.On the basis of the above studies and taking the 1,2-addition reaction of the carbonyl group in p-quinols as the starting point,this thesis extended the systematic studies to more extensive p-quinols,exploring their synthesis and new reactions and expanding their applications in organic synthesis.The thesis is divided into seven chapters.In the first chapter,the syntheses and reactions of p-quinols are reviewed and the thesis proposal is presented in chapter two.In the third chapter,the simple synthesis of 4-trifluoromethylated p-quinols has been explored based on the previous studies on the synthesis of 4-trifluoromethylated p-quinol ethers.In the fourth chapter,based on the easily formation of N-aryl imnium ion from 4-trifluoromethylated p-quinols and cyclic amines,a series of propargyl amines were synthesized from the reaction of cyclic amines with 4-trifluoromethylated p-quinols under copper(II)catalyzed redox-neutral conditions.This method has the advantages such as short reaction time and good regioselectivities.In the fifth chapter,the ring-opening/coupling reaction of the N-aryl imnium ion,which synthesized from 4-trifluoromethylated p-quinols and cyclic amines similar to its generation in chapter 4,has been investigated.As a result,a series of trifluoromethylated arylamines were synthesized and the mechanism has been further studied.In chapter 6,the [4 + 2] cyclization reactions of the generated N-aryl imnium ion have been investigated.Some trifluoromethylated natural product analogues such as incargranine B and seneciobipyrrolidine analogues have been synthesized.p,p '-Dibenzene(a kind of benzene dimmers),which are difficult to be synthesized using traditional methods,could also be obtained in good yields.In chapter 7,the propargyl unit was introduced into p-quinols.Their reactions with ?-oxo ketene dithioacetals,which acted as the bis-nucleophiles,have been investigated.A series of polysubstituted thiophenes were synthesized efficiently and rapidly.