Studies On The Synthesis Of Tricyclo[6.3.1.0^1,5]Dodecane Skeleton And ?-Arylation Reaction Of Oxindoles

Tricyclo[6.3.1.0^1,5]dodecane skeleton is found in many bioactive natural products.A concise and efficient synthetic strategy toward tricyclododecane skeleton is vital for the total synthesis of clovane-type natural product.Our group has focused on the study of semipinacol rearrangement since 1996.In continuation of this subject,we have tried to synthesize the tricyclo[6.3.1.0^1,5]dodecane skeleton through semipinacol rearrangment as the key step.Additonally,transition metal-catalyzed direct?-arylation of carbonyl compounds has emerged as a powerful methodology for the formation of quaternary carbon center and construction of skeleton of natural products.we have tried the application of our chiral ligand in the?-arylation of oxindole.The four following parts in this thesis are mainly included:1.Background of Tricyclo[6.3.1.0^1,5]dodecane skeleton synthesis was introduced.The recent development of construction strategies for such skeletons was briefly described in this section.2.Strategic applications of pinacol-type rearrangement were reviewed in the total synthesis of some natural products.In this part,the advantage of pinacol-type rearrangement was demonstrated in the total synthesis of natural products,such as ingenol?lingzhiol and?+?-sieboldine A.3.The construction of tricyclo[6.3.1.0^1,5]dodecane skeleton by intramolecular tandem semipinacol rearrangement has been designed and tested.To investigate the possibility of the key tandem Semipinacol rearrangement/Mukaiyama aldol reaction induced by epoxide ring-opening or oxidative coupling,two precursors have been designed and synthesized.4.The direct palladium-catalyzed?-arylation of oxindole has been described.To investigate the application of our chiral ligand,the direct?-arylation between oxindole and 2-bromopyridine was elaborated.