Synthesis Of Cyclobutane Derivatives Oxidative Cyclization By Iodine And Hypervalent Iodine

In this thesis, green chemical method of the solvent-free and solid phase grindingwas applied for synthesis of1,4-diaryl acyl-2,2-diester–3-aryl cyclobutane.First, the Micheal reactions of2-substituted malonate and chalcone derivativeswere studied. The results indicated that the Micheal reactions of malonic acid diethylester, malonic acid dibenzyl esters with chalcone derivatives（in addition to attachingon CH3O group）proceeded very well and gave the corresponding products in goodyields; and malonic acid dimethyl ester does not react in the screening of conditions.Second, the oxidative cyclization reaction of1,6-diaryl-3,3-diester-4-aryl-1,6-dione to cyclobutane derivatives catalyzed by I₂or PhIO were studied in detail. Byscreening the reaction conditions，such as temperature, oxidizing agents, base,solvents and so on，the results indicated that methanol was a most favorable solvent,and K₂CO₃was a favorable base, and iodine or hypervalent iodine was proved aneffective oxidate for the cyclization of1,6-diaryl-3,3-diester-4-aryl-1,6-dione togenerate the corresponding cyclobutane derivatives. Aryl ketones withelectron-donating group was favorite the oxidative cyclization reactions, andelectron-withdrawing substituted depressed the reaction and resulting in the oxidativecyclization reaction can not be occurred.