The Synthesis Of Phyllanthusols Analog Glycogen And The Synthesis Of Pyridine Directing Group And The Study Of CH Activation

This dissertation is divided into two parts.The first part reported the synthesis of the glycosyl of highly oxygenated nonbisabolane compounds,and the second part discribed the synthesis of the class of compounds with pyridine and quinoline directing groups and its application research in the field of C-H activation.Highly oxygenated nonbisabolane compounds are found in the Phyllanthus emblica Linn.,not common in nature,but they showed some bio-activities as insecticide,anti-inflammatory,antibacterial and anticancer activities.These compounds belong to sesquiterpenoids with special spiral ketal structure.Phyllaemblicins A and B from Phyllanthus emblica Linn are the phyllanthusol analogues,and can be hydrolyzed to aglycone and glycosyl.The later plays a great importance on the biological activity and pharmacological activity.The first part of the dissertation reported the synthesis of the glycosyl part of Phyllaemblicins B.The glycosyl is a disaccharide formed by the glucose molecules connected with 2-hydroxyl of one glucose and 1-hydroxyl of another glucose.The donor of glycosyl can be synthesized by trichloroacetonitrile activating the designated site of the glucose.The key problem of the acceptor synthesis is to selectively activate the 2-hydroxyl of glucose so that it could be linked with 1-hydroxyl of another glucose.We made a series of explorations and realized the selective protection using metal organic tin compound,dibutyltin oxide.We also made some simple connection attempts of the donor and acceptor.C-H bond is the simplest structure in organic chemistry,the activation of which can achieve economical,efficient and simple method to build molecular skeleton.Stereoselectivity has always been a key issue in the activation of the C-H bond.It is generally necessary to introduce the directing group into the activated molecule in order to achieve stereoselectivity.According to previous reports,the nitrogen-containing groups are often used as the directing group in the activation of C-H bonds.This part of the dissertation reported the activation of sp2 and sp3 C-H bonds by synthesizing substrates that introduced 2-pyridine directing groups.Firstly,tert-butylamine was modified by N-proteation,allylic reaction and fellowed with ozonation.After that,the keyprecursor compounds were obtained by induction of(S)-(-)-2-Methyl-2-propanesulfinamide and carbon-nitrogen double bond Micheal reactions,Finally,4 substrates for activating C-H bonds research were synthesized and some simple C-H activation reactions were studied.The related compounds synthesized in the two parts of this dissertation have been confirmed by NMR spectroscopy.