Functionalization Of Olefines,Alkynes And ?,?-unsaturated Acids

Unsaturated compounds containing–C=C–and–C?C–components that can undergo various types of reactions are important organic compounds in organic synthesis due to the unsaturated carbon-carbon double and triple bonds.In addition,they are widely used in the synthesis of natural products,drugs and materials.My doctoral research focuses on functionalization of olefines,alkynes and?,?-unsaturated acids.?1?A copper-catalyzed domino Suzuki coupling between 1,1-dibromo-1-styrenes and arylboronic acids was described in the second chapter.8-Hydroxylquinoline was found to be the best ligand.A series of diaryl acetylenes as well as a representative eneyne can be synthesized via this methodology.?2?Direct synthesis of cinnamic amides from cinnamic acids and formides was reported in the third chapter.CuSO₄ was used as the efficient catalyst and di-tert-butyl peroxide?DTBP?was used as the proper oxidant.Various cinnamic amides were obtained in excellent yields.Futhermore,a radical pathway and the decarboxylation of cinnamic acid might be involved in the mechanism.?3?A decarboxylative Csp³-H functionalization of N-substituted amides with cinnamic acid catalyzed by copper catalyst was depicted in the forth chapter.Copper oxide and DTBP mediate acetamide to generate acetamidomethyl radical,which adds to the double bond of cinnamic acid,followed by decarboxylation and subsequent generation of N-cinnamyl actamide.?4?A multicomponent reaction of phenyl acetylene,tert-butyl nitrite and TEMPO was reported in the fifth chapter.The addition of a nitro radical to the triple bond of phenyl acetylene generates a vinyl radical in situ,which was trapped by TEMPO by the first time.?5?Based on our group's research about decarboxylation and the nitroaminoxylation of terminal alkynes,a silver-catalyzed decarboxylative nitroaminoxylation of propiolic acids was studied in the sixth chapter.The silver catalyst shows great efficiency that the amount of silver oxide can be decreased to 1mol%while the nitroaminoxylative products were still furnished in good yields.?6?A cycloaddtion of diphenyl acetylene with benzocyclobutanol was developed in the seventh chapter.The ring-openning of benzocyclobutanol generates an iridium complex in situ.The resulted iridium complex adds to the diphenyl acetylene and the carbonyl group in order.Finally,aromatization of the intermediate gave a seies of polycyclic aromatic hydrocarbons.