Copper(Ⅰ)-catalyzed Synthesis Of Unsymmetrical Aryl Thioethers/Ethers Compounds From Dipyrimidinyl Disulfides

Organic sulfides present in many biologically active compounds,and many aryl thioether skeletons especially are the key structures of medicines.Therefore,aryl thioethers are widely used in the pharmaceutical,industry,agriculture,dyestuff industry,and materials science.Aryl thioethers,as intermediates in organic synthesis,play a vital role in the field of organic chemistry.The synthesis of the aryl thioether become one of the hot topics in the field of synthesis research.C–S coupling reactions of sulfur-containing reagents with other compounds are important methods to synthesize the aryl thioethers.Nowadays,stable and low-odour disulfides have replaced the volatile sulfur phenolic compounds in the air as sulfur reagents in the synthesis of thioether compounds.This thesis reviewed the synthesis methods of aryl sulfides.Meanwhile,the copper（I）promoted C-S、C-O coupling reactions have been developed using dipyrimidinyl disulfides and aryl boronic acids,phenols/thiophenols for the preparation of aryl thioethers and ethers.The main thesis and results are as follows:1.（2-chlorobenzoyloxy）copper（I）-catalyzed cross-couplings of di（hetero）aryl disulfides with arylboronic acids have been developed,providing C–S cross-coupling products with excellent yields under base-free conditions.The compounds were confirmed by¹H NMR、¹³C NMR and HRMS.The method allows the synthesis of pyrimidinyl thioethers as well as other aryl/pyridyl containing thioethers with general satisfactory results,which provides a novel procedure for synthesizing the aryl thioethers.2.We further discussed the reaction of dipyrimidinyl disulfides.CuCl-promoted C-O/C-S cross-couplings of dipyrimidinyl disulfides with phenols/thiophenols have been developed.The products were confirmed by¹H NMR、¹³C NMR and HRMS.The reaction avoided the use of palladium and ligand,involving C–S cleavage of disulfides which are harder to break.However,The experiment was carried out under inert gas and its substrates were poor tolerated.