Oxidative Carbonylation Of Arylhydrazines And Synthesis Of Ynamides

Amide,ester and ketone compounds could be synthesis though transition metal catalyzed oxidation carbonylation reaction due to its high catalytic efficiency,good selectivity and mild reaction conditions.With the rapid development of metal organic chemistry,palladium-catalyzed oxidation carbonylation reaction has also been developed rapidly and made great progress.Therefore,it is necessary to develop a new and green oxidation carbonylation by palladium-catalyzed.Because of the unique structural properties,ynamide is one of the key synthons in the synthesis of nature products and pharmaceutical molecules.So the development of ynamide chemistry,especially the synthesis methods of ynamides,has been one of the research hot topics in synthetic chemistry.This thesis is divided into the following two parts.Part one,aryl ester and pyrazole derivatives were synthesized via palladium-catalyzed oxidative carbonylation reaction of aryl hydrazine.Part two,a novel approach to ynamides using N-methyl p-toluene sulfonamide and 1,1-dichloroalkene as substrates was developed.The main contents are as follows:1.We developed a novel oxidation carbonylation reaction to afford aryl esters,using Pd Cl₂?dppp?as catalyst,oxygen as oxidant,carbon monoxide as carbonyl source.2.We developed a regioselective approach to afford trisubstituted pyrazoles via palladium-catalyzed oxidative sonogashira-carbonylation of arylhydrazines.The formation of trisubstituted pyrazoles involves a sequential C-N bond cleavage,carbonylation,Sonogashira coupling,Michael addition,and intramolecular condensation cyclization tandem process.3.We developed a transition-metal free method for the synthesis of ynamides using N-methyl p-toluene sulfonamide as nucleophile and 1,2-dichloroalkene as the precursor of alkyne...