Samarium-Promoted Addition Between Aroyl Chlorides And α,β-Unsaturated Carbonyl Compounds

The dissertation consists of three chapters. In the first chapter, the applications of samarium reagents and Michael addition reaction are briefly described in respective, which include metallic samarium, samarium(II) iodide, samarium(III) iodide, and allyl samarium bromide, etc.. The reactions promoted by Sm in DMF and other metals in DMF are discussed as well. In addition, we also expounds various Michael addition reaction, and the related literature proper references.The second chapter described samarium-promoted Michael addition between aroyl chlorides andα,β-unsaturated carbonyl compounds, including (1) samarium-promoted Michael addition between aroyl chlorides and chalconesthe; (2) reaction media, temperature, time, the ratio of raw materials and structure of the substrate to influence the reaction; (3) samarium-promoted organic reaction between aroyl chlorides and cinnamate (4) a possible mechanism was assumed. It has been discovered a novel Michael addition type reaction between aroyl chlorides and chalcones realized in the presence of samarium metal when N,N-dimethylformamide was used as a solvent. The Michael addition reaction is likely to happen between chalcones and benzoyl chloride, toluoyl chloride, 4-chlorohenzoyl chloride, 4-fluoride benzoyl chloride. A variety of 1,4-diketones were thereby synthesized in moderate to good yields. This reaction cannot happened between anisoyl chloride and chalcones, but generated the anisoyl chlorides self coupling reaction. In addition, maybe Sm-promoted bis-acylation of the carbon-carbon double bond addition of cinnamate with aroyl chlorides in DMF. The distribution of yield and affecting actors were also discussed in detail and summarized.The third chapter described the coupling and dehydration reactions ofα-bromohypnones promoted by samarium triiodide and p-toluene sulfonic acid were studied in DMF . A variety ofα-bromohypnones as reaction substrates, and generated different new product. Reaction mechanism has yet to be explored further. The type of this reaction is unique, which offers the new application of samarium(III) iodide reagent in organic synthesis.The preparations and the operation procedures were described in detail in the Experimental Section, and the relative literatures are appended. All the compounds obtained in the study introduced in this dissertation were characterized by ¹H NMR, ¹³C NMR, IR etc., and their corresponding spectra are attached at the final of this dissertation.