Synthesis Of α-carbonyl Amides,α-amino Amides,β-nitrylamines And α-siloxyl-α-alkooxy Carbonyl Amides Using Carbamoylsilanes As An Amide Source

Amides and substituted amides have a wide range of applications and applications in pharmaceuticals,polymers,cosmetics,electronic materials,and biologically active natural products,and are important synthetic intermediates in organic synthesis.The amide bond is an important chemical bond that constitutes peptides and proteins.Therefore,it is of great theoretical significance and application value to study the synthesis of amides and substituted amides.In this paper,four aspects of synthetic methods were studied and four new synthetic methods were proposed.First,synthesis of α-carbonyl amide.Alpha-carbonyl amide is an important intermediate in organic synthesis and plays an important role in the conversion of different functional groups and the synthesis of important heterocyclic compounds.It can be used as an anti-viral,multi-enzyme and receptor inhibitor.In the past few decades,methods for synthesizing α-carbonyl amide have been explored,and some synthetic methods have been discovered,but there are some disadvantages,such as the use of toxic transition metal catalysts,organic oxidants or oxygen,dangerous CO gas,complicated experimental operation,low yield rate and toxic by-products.Therefore,it is necessary to study a new synthesis method of α-carbonyl amide.In this paper,a new method for the synthesis of α-carbonyl amide by reaction of carbamoylsilane I with a carboxylic acid ester was studied.The amino acid group was directly introduced into the substrate molecule to convert the carboxylic acid ester into α-carbonyl amide.The reaction was analyzed from the electronic effect,induced effect and spatial effect,and the possible reaction mechanism was proposed.Second,the synthesis of α-aminoamide.Alpha-amino amide is a basic structural unit of polypeptides and proteins,and its structure is found in a large number of natural products and drug molecules,and thus plays an important role in chemistry,biochemistry,and pharmacy.In the past few decades,more studies have been carried out on multi-component Ugi reactions with amines,carboxylic acids,aldehydes and isonitriles to achieve the synthesis of α-aminoamides.The disadvantage of this method is that it is difficult to deprotect the amino group.The residue of nitrile is difficult to control the uniqueness of a single substitution on the amide nitrogen atom.Although the method has been continuously improved to obtain a certain effect,it is difficult to avoid the defects of the reaction itself.In this paper,a new method for the reaction of N-phenylsulfonyl imine with α-aminoamide was studied using carbamoylsilane as the amide source.We reacted with carbamoylsilane IV and N-benzenesulfonyl imine to form a sulfonyl protected α-aminoamide,which converted 8 different structures of N-benzenesulfonyl imide,discussed the electronic effect,induced The effect of the effect on the reaction is proposed.Third,reaction of ethyl α-nitroenoate with carbamoylsilane II.In recent years,phenylacetamides have been gradually favored by people because of their unique biological activities and broad application prospects.It plays an important role in medicine,food and cosmetics.Previously,our group synthesized phenylacetamide using carbamoylsilane and benzyl halide under the catalysis of palladium,but it used expensive catalysts and was polluted by the environment,which did not meet the requirements of modern green chemistry.Therefore,it is necessary to develop a simple and efficient synthetic route.In this paper,a new synthetic method for the reaction of carbamoylsilane II with ethyl α-nitroenoate to form phenylacetamide derivatives was studied.Six products were synthesized by this method,and the influencing factors of the reaction were discussed.Fourth,reaction of α-carbonyl ester with carbamoylsilane III and IV.In organic synthesis,α-alkoxycarbonylamide derivatives are intermediates and common structural units of many natural products and pharmaceutical synthesis,andare also an important class of synthetic targets,and thus methods for synthesizingα-alkoxycarbonylamide derivatives.It has been extensively studied,and a common synthetic method is oxidation of α-alkoxycarbonylamide or direct catalytic oxidation with a transition metal.However,these methods have some disadvantages,namely the effect of the use of organic oxidants on other groups,the high cost of heavy metal catalysts,the difficulty in separating toxic by-products,and the limitations of the range of use of this method.Therefore,it is necessary to study a new synthesis method of an α-alkoxycarbonylamide derivative.In this paper,a new method for the synthesis of α-siloxy-α-alkoxycarbonylamide was studied by reacting carbamoylsilane III,IV with α-carbonyl ester,and the conversion of six substrates was realized.The influencing factors of the reaction were discussed,proposed a possible mechanism.The method has mild reaction conditions,simple operation and no pollution,and provides a new route for synthesizingα-siloxy-α-alkoxycarbonylamide.In summary,the acylation reaction was carried out using carbamoylsilane as the amide source,and four new synthetic methods were discovered.Using these four methods,37 substituted amide derivatives were synthesized,which made these methods applicable.Different substituents were extended,and the scope and influencing factors of the reaction were explored,which provided valuable information for practical organic synthesis and drug synthesis applications.