Metal-Catalyzed Organic Synthesis Reactions Based On Molybdenum Hexacarbonyl As A New Carbonyl Source

In organic synthesis,it is very important to synthesize commercial chemicals from cheap chemical raw materials.The carbonylation reaction explored in this paper is one of the industrial core technologies for the synthesis of various chemical products in daily life.The presence of carbonyl atmosphere is an essential prerequisite for carbonylation.In the traditional method,carbon monoxide is used to provide carbonyl source,but carbon monoxide itself is tasteless but toxic.At the same time,a reactor with high pressure resistance and good air tightness is needed for the reaction.Due to the unique chemical properties of carbon monoxide and the relatively harsh experimental conditions,the research progress of using carbon monoxide as carbonyl source in carbonylation reaction is limited.In this paper,Mo(CO)₆,a solid carbonyl source,was found and proposed to mediate related reactions,which effectively solved the above limitations and provided a convenient and safe carbonylation method.Objective to obtain a convenient and safe method of carbonylation.In the first part of the work,after theoretical reaction calculation,molybdenum hexacarbonyl was explored as the carbonyl source to participate in the intercalation reaction of biaromatic substrates,and the selectivity was screened.In the second part,molybdenum hexacarbonyl was used as the carbonyl source,and the selectivity of intramolecular N-heterocyclic synthesis was successfully explored under the catalysis of metal.A chemical reaction system without using gaseous carbon monoxide to provide carbonyl source was developed,which provided a safe,simple and effective synthesis method for the production of pesticides,dyes,pharmaceuticals and other industrial products and the synthesis of important intermediates.The main work are as follows:1)In Chapter 2,the selective carbonylation of carbonyl group was studied.The reaction mechanism was explored by theoretical calculation,and the mechanism of carbonylation cycle was proposed.Molybdenum hexacarbonyl,a new type of non gaseous carbonyl source,was used to participate in the intercalation reaction.In the experimental verification scheme,molybdenum hexacarbonyl was used to participate in the reaction,and bis-(1,5-cyclooctadiene)nickel was used as catalyst to avoid the experimental limitation caused by the use of gaseous carbon monoxide.2)In the third chapter,molybdenum hexacarbonyl as a carbonyl source is involved in the selective synthesis of intramolecular N-heterocyclic compounds.In the research process of intramolecular N-Heterocycle synthesis,hexacarbonyl molybdenum was also used as a new carbon source instead of gaseous carbon monoxide to participate in the intramolecular cyclization reaction.By changing the reaction conditions,the best reaction conditions were obtained under laboratory conditions;the substrate expansion part not only screened the influence of aromatic substrate substituent changes(electronic effect,steric hindrance effect)on the yield of the reaction,but also screened the yield of N-heterocycles generated by intramolecular cyclization of similar substrate derivatives under the best conditions,and obtained a variety of different N-heterocyclic scaffolds Precursors.