Asymmetric Formation And Cleavage Of Allylic C-N Bonds And Vicinal Difunctionalization Of C=N Bonds

C-N bonds and C=N bonds are common chemical bonds and widely exist in organic molecules, pharmaceutical molecules, and natural products. The research of their formation and cleavage has great theoretical significance and application value. We used palladium-catalyzed allylic reactions to realize some formation and cleavage reactions of C-N bonds. Using arynes to activate C=N bonds which can achieve the reactions of their vicinal difunctionalization.This dissertation includes six chapters.Chapter one:Introduction of progress in palladium-catalyzed allylic reactionsWe first introduced substitution reactions of allylic alcohols and allylic amines. Chiral allylic alcohols and chiral primary allylic amines have the advantage of atom-economy and easy prepared, the meaning of developing their chiral transfer reactions is obvious. Then we introduced the types of electrophilic reagents in palladium-catalyzed allylic reactions. Different kinds of electrophilic reagents have their own advantages which provide guideline for us to develop new electrophilic reagent. At last, we introduced palladium-catalyzed allylic kinetic resolution reactions. The nucleophilic reagents in these reactions currently are only carbon type and sulfur type. The study of new nucleophilic reagent possesses great value.Chapter two:Stereospecific allylic reactions of allylic alcohols with substituted hydrazinesChiral hydrazine compounds could be used as useful organic reagents, pharmaceutical molecules, and reaction materials. In order to broaden the synthesis methods of chiral allylic hydrazines, we developed the chiral transfer reactions of chiral allylic alcohols (a-substituent≠γ-substituent) with substituted hydrazines. The reaction reacted under room temperature and gave good results. The reaction product of phenylhydrazine was hydrazone and the reaction product of sulfonyl hydrazide was chiral allylic sulfone. The reaction byproduct is water which is environmental friendly.Chapter three:Palladium-catalyzed stereospecific allylic reactions of nitroacetates with chiral allylic aminesNitroacetates could transform to nitro, ester, amio acid, and ketone. We developed the reactions of nitroacetates with chiral primary allylic amines, the products could transform to chiral homoallylic nitro compounds and chiral homoallylic ester compounds. Many kinds of reaction substrates all could give preferable results. In addition, other types of active methylene nucleophilic reagents, such as cyano actetate and acetyl acetone, etc, can react with chiral primary allylic amine.Chapter four:Kinetic resolution of allylic hydrazines via sulfonyl hydrazidesWe developed the kinetic resolution reactions of allylic hydrazines with nucleophiles. Sulfonyl hydrazide is used as a sulfone source. When it was used as nucleophile with allylic hydrazine in kinetic resolution reaction, chiral allylic hydrazine and chiral allylic sulfone were obtained in moderate yields. The reaction selectivity factors up to 100. The substrate structure has a great influence on the reaction result. Finally, we tried derivatization reactions of chiral allylic hydrazine products.Chapter five:Three-component reactions of arynes with imines and protic nucleophilesArynes are important reaction intermediates which can occur various types of reactions, such as addition reaction, percyclic reaction, insertion reation, multicomponent reaction, etc. They have important research value. The nitrogen on imines can serve as nucleophiles to react with arynes. Trichloromethyl group is widely presented in natural products, the methods to introduce trichloromethyl group currently are limited. So we developed three-component reactions of arynes, imines, and chloroform to synthesis a-trichloromethyl amine products. When imines were prepared from aldehydes containing strong electron-withdrawing groups, the products were alkenes. Additionally, Acetonitrile and terminal alkyne could replace chloroform to react in this reaction.Chapter six:Three-component reactions of arynes with aromatic nitrogen-contained heterocycles and chloroformThe nitrogen on quinoline, isoquinoline, or pyridine can serve as nucleophilic reagents to react with arynes. So we developed three-component reactions of arynes, nitrogen-contained heterocycles, and chloroform. The products are dearomatization with vicinal difunctionalization of C=N bonds. Many kinds of nitrogen-contained heterocycles and various substituted arynes could react well. Replacing the chloroform of deuterated chloroform to study the reaction mechanism, The reaction mechanism form was judged according to the location of the deuterium hydrogen in product.