One-pot Procedure For The Synthesis Of α-ketoamides From Ethylarenes/α-oxocarboxylic Acids With Amines Under Mild Conditions

α-Ketoamides and their derivatives are widely found in natural products,biologically relevant molecules, drugs and drug candidates, and functional materials.moreover, they also serve as valuable precursors and synthetic intermediates for functional group transformations in synthetic organic chemistry. Due to their wide applications, the formation of α-ketoamides has attracted considerable attentions, and there has been a plethora of procedures developed for α-ketoamides synthesis starting from varied materials to provide carboxylic acid moieties for α-ketoamides. Nevertheless,most of them are multiple-step procedures and usually suffer from limited substrate scopes,using large excess of oxidation reagents, the application of transition/heavy-metal catalysts,harsh conditions, and low product yields. Therefore, developing atom-efficient and environmentally benign approaches especially for sustainable industrial applications is highly desirable.In this thesis, the author has developed two methods for the synthesis of an array ofα-ketoamides. One is the use of copper iodide as the catalyst and tert-butyl hydroperoxide as the oxidant, ethylarenes and amines are as the starting materials for amidation eactionds to prepare α-ketamides; The other one is an efficient one-pot procedure employing cyanuric chloride via chlorination of carboxylic acid and amines to synthesizeα-ketoamides. At the same time, the corresponding experiments on the substrates were found to have achieved satisfactory results. Compared to the previous results by other groups, these two methods developed in this thesis required no transisation/heavy metal catalysts for efficient synthesis of α-ketoamides under mild conditions. The reaction conditions of the two synthetic ways for the synthesis of α-ketoamides by using the principle of single variable to explore the optimum reaction conditions. The optimum conditions for the synthesis of α-ketoamides for former way is: ethylarenes 1.0mmol,amines 6.0mmol, The amount of catalyst CuI is 20 mol%, The amount of oxidant TBHP is 3.0equiv., the reaction temperature is 50 ℃, the reaction time is 24 h, etc; The other method of the optimal reaction conditions for the synthesis of α-ketoamides is: CH2Cl2 as reaction solvent, α-oxocarboxylic acids 0.5mmol, amines 1.0mmol, the amount of TCT is 1.0equiv., the amount of triethylamine is 1.0mmol, the reaction temperature is 25 ℃, the reaction time is10 min, etc. At the same time, we have carried on the substrate development and the mechanism discussion. The isolation product is characterized by 1H NMR, 13C NMR and IR spectral data.