Resolution Of Diketone And Total Synthesis Of The Sesquiterpene Aquatolide

This thesis comprises two chapters:(a)resolution of the 2,3:6,7-dibenzobicyclo[3.3.1]nona-2,6-diene-4,8-dione;(b)total synthesis of the sesquiterpene Aquatolide.The first chapter:highly efficient and practical resolution of the 2,3:6,7-dibenzobicyclo[3.3.1]nona-2,6-diene-4,8-dione and stereoselective synthesis of its chiral diamine derivatives.We developed a highly efficient and practical resolution method.We can resolve the diketone with commercially available enantiopure BINOL and the method performs very well for a multi-gram scale preparation of enantioenriched diketone.When carried out the resolution for a 50 gram scale,we got 85%total yields and 99%enantiopurity after one recrystallization.It is worth that the BINOL can be recovered in 95%yield with the enantiopurity being unchanged.To our excitement,we got a single crystal of the complex that helped us to confirm the absolute configuration.We also observed the strong hydrogen bonding between the carbonyl group and the phenolic hydroxyl from the single crystal(C=O…H-OAr).With the enantiopure diketone in hand,its diamine and diol derivatives were synthesized.The second chapter:total synthesis of the sesquiterpene Aquatolide.This chapter reported the total synthesis of Aquatolide in a 25 linear steps from the commercialized sodium cyclopentadienide.We developed two methods to synthesize the Aquatolide.We planned the Wolff ring contraction and late-stage Nozaki-Hiyama-Kishi medium-ring formation as the two key steps.During the research,a substrate-dependent dimethylation was studied.We developed a TEMPO and 2-Hydroxy-2-azaadaMantane sequentially catalyzed lactonization reaction.To selective reduction of carboxylic acid to alcohol,a mixed-anhydride strategy was studied after the Wolff rearrangement was performed.Finally,the eight-numbered medium ring was constructed via the Nozaki-Hiyama-Kishi reaction.