Studies On The Metal-free Synthesis Of α,β-unsaturated Carbonyl Compounds And 1,3-dicarbonyl Compounds Via α-H Activation Of Carbonyl Group

Transition metal catalysts are expensive;their use increases not only the reaction cost,but also the work-up difficult because the metal residue would lead to the decrease of products in quality.The metal-free reactions can well solve these issues described above and attract much attention of synthet ic chemists.The manuscript focuses on the activation of carbonylα-H to carry out scientific research,two green synthesis methods of carbonyl co mpounds have been developed:The manuscript focuses on the metal-free synthesis ofα,β-unsaturated carbonyl compounds and 1,3-dicarbonyl compounds via the activation of carbonylα-H.The specific contents and results come as follows:（1）α,β-unsaturated carbonyl compounds are widely occurring in natural products and drugs.They are also the important synthetic intermediates of many organic reactions.Therefore,development of efficient methods for their preparation is of great significance.We disclosed a facile catalytic system with the use of I₂/KI as the catalyst and DMSO as the solvent and mild oxidant.The reaction is carried out in one pot under a simple condition,overcoming the issues in terms of multi-step operation,the use of strong oxidants and（or）transition metal catalysts in conventional methods.The reaction showed high functional group tolerance and was scalable.These results demonstrated the synthetic value o f this reaction.（2）Diketones are important intermediates for the synthesis of bioactive and functional materials.Their traditional synthesis depends on the reaction of organohalides with dicarbonyl compounds through copper catalysis,requiring long reaction time and pre-preparation of organohalides.In this manuscript,a simple method throughα-C-H acylation of ketones using amides as the acylating reagent was demonstrated.The reaction conditions were simple and easy to operate.