Studies On Copper-catalyzed C-S,C-O Forming Reactions And Related Tandem Reaction

Organic compounds containing C-O and C-S bonds widely exist in pesticides,pharmaceutical intermediates and natural products.Employing copper-catalyzed coupling reactions to construct C-S and C-O bond is important strategy in the synthesis of various organic heterocycles and other organic products containg heteroatom functional groups.This thesis is focused on the copper-catalyzed coupling reactions,including Ullmann type cross coupling reaction and C-H activation as main tactic,designed and established different types of methods in constructing C-O/C-S bonds towards the synthesis of diverse organic product,and mainly covers three different sections.Firstly,we investigated the copper-catalyzed C-H sulfonylation reactions based on the in situ installation of directing group.By employing directly 8-aminoquinoline(AQ),aroyl chlorides and thiophenols as starting materials,the AQ-directed aryl C-H sulfenylation of the benzamides via the catalysis of copper(II)acetate.By modifying the reactions,the in situ generated benzmides could selectively undergo mono-and di-sulfenylation on the two symmetrical C-H bonds,providing the 2-sulfenylated and 2,6-disulfenylated benzamides,respectively.Subsequently,by utilizing sulfonyl hydrazines as alterantive S sources and Cu I catalyst,we accomplished the tandem reactions of AQ,acyl chlorides and 8-aminoquinoline for the directed directing group installation and selective mono-C-H sufenylation toward the synthesis of thioester containing benzamides.Besides the selective reaction pathway,the other advantage of this method is the employment of ordorless thio sources which are friendly to the operator.Finally,we studied the copper-catalyzed tandem aryl-halogen hydroxylation and double Williamson etherification reactions of o-halobenzoic acids,dichloromethane and hydroxyl base.Thus,A new method for the synthesis of benzo[d][1,3]dioxin-4-ones has been developed.The reactions feature simple and mild reactions conditions,commercially available and simple starting materials and catalyst,which provides a practical new route for the synthesis of these useful hererocylic compounds.