Study On The Construction Of Indeno[1,2-c]thiophene,1-Indanone,Benzo[b]fluorene And 2-Naphthalene Skeletones Via Domino Cyclization Of 1,n-Enynes

Domino cyclization reaction is one of the frontiers and hotspots in organic chemistry,which has been widely used in the synthesis of natural products,original heterocyclic framework and so on.During which,domino cyclization reactions of 1,n-enynes have been attracted considerable attention In recent years.In this dissertation,metal-catalyzed or radical-triggered domino cyclization of 1,n-enynes were investigated,which provided fused ring compounds in simple and efficient way.The details are as follows:In the first part,the characteristics of domino cyclization reaction are introduced,and the research background regarding metal-catalyzed or radical-induced domino cyclization of 1,n-enyne substrates are also presented.Furthermore,on the basis of these report surveys,the topic selection,significance and novelty of this dissertation were also described.In the second part,a new copper-catalyzed domino cyclization reaction for the synthesis of indeno[1,2-c]thiophene derivatives was described.This CuCl2-catalyzed reaction of 1,6-enynes with K2 S as sulfur source in the presence of diisopropylamine accessed highly substituted indeno[1,2-c]thiophene derivatives through a Michael addition/5-exo-dig cyclization/isomerization/dehydrogenation process.The transformatImation enables the direct construction of C-S and C-C bonds and features atomic economy,environment-friendly,efficient bond-forming events.In the third part a new radical-induced domino cyclization reaction for the synthesis of 1-indenone derivatives was developed.The reaction of 1,6-enynes with terminal alkene uint and diphenoxyphosphine was carried out by using tert-butyl peroxybenzoate(TBPB)as the oxidant,by which a series of 1-indenone derivatives were synthesized through α,β-conjugated addition/5-exo-dig cyclization process with simultaneous formation of C-P,C-C and C-H bonds.The reaction has the advantages of simple operation,mild reaction condition,and efficient annulation.In the fourth part,a new copper/rhodium co-catalyzed domino cyclization reaction for the selective synthesis of benzo[b]fluorenes and naphthalenes was presented.The Cu/Rh co-catalyed reactions of 1,5-enynes with terminal alkynes and ethyl ?-aryl diazoacetate were carried out by using Ph I(OAc)2 as the oxidant,enabling de-diazotization-metal carbine formation/ligand exchange/insertion-migration/enolizati-on/[4+2] cycloaddition/dehydrogenation/tautomerization sequence to furnish structurally diverse benzo[b]fluorenes whereas benzofluorene derivatives were obtained through the reaction of 1,5-enynes with ethyl diazoacetate(and ?-diazo aryl ketones)which involved de-diazotization-metal carbine formation/ligand exchange/insertionmigration/enolization/pericyclic reactions/tautomerization process.These experimental results indicated that the substituents on the ?-diazo carbonyls affect the selevity of reaction.Furthermore,these reactions feature efficient annulation and highly functional group compatibility.