Iodine-mediated Construction Of Sulfocompounds And Palladium/Copper-Catalyzed Synthesis Of Substituedpyridines

Non-metallic iodine shows a variety of properties in the chemical reaction for it's multi-valence state,mainly reflected in the redox,as well as a variety of addition reaction.And iodine is low cost and environment friendly.Through the above characteristics of iodine,we have done some studies on iodine-mediated difunctionalization of allenes,iodine-catalyzed oxidation of homopropargylic alcohols,iodine-catalyzed decarboxylation of?-Amino Acids to construct C/S,C-N bonds and so on.Transition metal palladium/copper used as a commonly metal catalyst,using their synergistic interaction with the oxygen,a series of substituted pyridines were synthesized through phenylaldehyde and allylamine/1,3-Propanediamine,this work have supplemented to the methods of pyridines synthesis besides former types of coupling reaction?Suzuki reaction,Stille reaction,Negishi coupling?.Part?:Iodine-mediated difunctionalization of allenesNovel and metal-free strategies for iodothiocyanation/nitration of allenes with potassium thiocyanate/silver nitrite via C-X?SCN,ONO₂,I?bonds formation have been described.In this process,potassium thiocyanate/silver nitrite and molecular iodine are used as the source of SCN,ONO₂ and iodine to provide desired products in moderate to good yields with high stereoselectivity.Part?:synthesize substituted sulfanylfurans and?-sulfonated naphthalenes from homopropargylic alcohols and sulfonyl hydrazidesA sulfenylation and thiolation/cyclization reaction has been developed for the synthesis of sulfanylfurans and?-sulfonated naphthalenes.In this transformation,various groups on homopropargylic alcohols and sulfonylhydrazides proceed smoothly and the desired sulfanylfurans and?-sulfonated naphthalenes are obtained in moderate to good yields.Part?:Iodine-catalyzed decarboxylative?-amino acidsWe used iodine-catalyzed?-amino acids for decarboxylation and sulfonic acid radicals conbined with the intermediates via free radical addition,which was formed by TBHP oxidation of sodium sulfoxide.In the whole process,the nitrogen-atoms played a great electron transfer effect,under the appropriate reaction conditions,a variety of target products were afforded in the modrate yields.Part?:Pd?OAc?₂/Cu?OAc?₂ catalyzed synthesis of substituted pyridinesA novel and efficient Pd?OAc?₂/Cu?OAc?₂ catalyzed oxidative tandem cyclization methods for synthesis 3-aryl pyridines of simple 3-aminopropene/1,3-diaminopropane and aldehydes have been developed.In this reaction,a series of desired 3-aryl pyridines are afforded in moderate yields via C-C/C-N bonds formation and 6-endo/exo-trig cyclization.