Studies On The Tandem Reaction Of Cyclohexadienone-Containing Spirolactams By Asymmetric Desymmetrization

Cyclohexadienones have stimulated a great deal of interest of synthetic chemists due to its unique multifunctional feature. Recently, the compounds with this kind of structural characteristic not only are tactically involved in the synthetic studies of many bioactive molecules, also become an important object in the development of chiral methodologies.Focusing on the design of catalytic asymmetric reactions of cyclohexadienones as well as with the aim of the synthesis of multifunctional Biichi’s ketone, this thesis mainly deals with the study of a model tandem reaction of the cyclohexadienone-containing spirolactams via asymmetric desymmetrization. This asymmetric catalytic model reaction lays a foundation for the development of new synthetic method for various functionalized chiral Buchi’s ketones, preliminarily showing an important significance in asymmetric synthesis of Strychnos alkaloids and Aspidospermine alkaloids. This thesis is mainly supported by the following three parts:The first chapter:A brief introduction to the structure types of cyclohexadienones as well as the progress in achiral, racemic and asymmetric methodologies was presented.The second chapter:With the progress in the asymmetric synthesis of Buchi’s ketone, the model tandem reaction of cyclohexadienone-containing spirolactams was investigated under the organocatalysis. During this study, various influencing factors (e.g., catalysts, solvents, temperature, additives) were preliminarily investigated. Certainly, these results to some extent provide some useful exploration in the development of asymmetric catalytic tandem reaction of cyclohexadienones.The third chapter:The details on the related experimental procedures were described, in which the optimization of the reaction conditions, the preparation of substrates and some catalysts as well as the analytical data of compounds were included.