The Study On Coupling Reactions Catalyzed By Copper(i)/samarium

The dissertation consists of two chapters. In the first chapter, the applications of samarium reagents and copper salts in organic synthesis are briefly described in respective, which include metallic samarium, samarium(II) iodide, samarium(III) iodide, samarium/auxiliaries and allylsamarium bromide, etc.. In addition, the reactions promoted by other metals in DMF are discussed as well. The second chapter described the self-coupling condensation of aromatic aldehydes catalyzed by copper(I)-samarium, including (1) the self-coupling condensation of aromatic aldehydes catalyzed by Sm/CuI; (2) the oxidization of benzoins to benzils in the condensation mixture; (3) the self-coupling condensation of aromatic aldehydes catalyzed by Sm/CuCl/KI; (4) the self-coupling condensation of aromatic aldehydes catalyzed by other copper salts; (5) a possible mechanism was assumed. 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, GC-MS, HPLC etc., and their corresponding spectra are attached at the final of this dissertation.Aromatic aldehydes react self-condensation readily when promoted by samarium metal in THF with copper(I) iodide or copper(I) chloride / potassium iodide as a co-catalyst, to afford benzoins in good yields. In some cases, benzils were also obtained as the unexpected byproducts. The formation of benzils was explained. The catalytic reactivities of a variety of copper salts were investigated. The distribution of yield and affecting actors were also discussed in detail and summarized.This is the first attempt to search for a practical and efficient co-catalyst for expanding the applications of samarium reagents in our group. Excluding the pinacol-coupling-type reactions of aldehydes, this transformation constitutes the first example in which a new C?C bond is promoted by samarium in the presence of copper salt. Besides, the condensation is also a highly efficient method for the synthesis of benzoins from aromatic aldehydes with easier operation.