Tertiary Amine And Triphenylphosphine Promoted Multicpmponent Reaction For Spiro Compounds

Spirocyclic compounds are one special type of organic compounds with two single rings sharing one carbon atom.They can be divided into spiro carbocyclic compounds and spiro heterocyclic compounds according to the different atoms in the cycles.Nowdays,spiro compounds have attracted much attention due to their important biological activities such as anti-tumor,anti-fungal drugs,etc.The cycloaddition reaction catalyzed by nucleophilic tertiary amines and phosphines were often employed to prepare versatile cyclic compounds due to its short reaction period,versatile activity and high yields.In this paper,a series of spiro compounds were successfully synthesized by nucleophilic tertiary amines and phosphines promoted multicomponent reaction of electron-deficient alkynes and arylidene dicarbonyl compounds.The three-component reaction of aza-arenes such as isoquinoline?quinolone,4-dimethylam-inopyridine?wtih dimethyl acetylenedicarboxylate and arylidene dicarbonyl compounds have been investigated.Therefore,a series of spiro[indoline-3,1'-pyrido[2,1-a]iso-quinoline],spiro[indene-2,4'-pyrido[1,2-a]quinoline]and dihydroindeno[1,2-b]pyrene derivatives were successf-ully prepared.All the new products were characterized by IR,¹H NMR,?13?C NMR and HRMS spectroscopy.The single structure of five compounds were determined by X-ray diffiraction method.The experimental results showed that isoquinoline and quinoline participated in the reaction to give spiro-indoline-pyridine,whileas 4-dimethylaminopyridine participates in the reaction to give dihydroindeno[1,2-b]pyrene derivatives.The three-component reaction of triphenylphosphine,dimethyl hex-2-en-4-ynedioate and arylidene N,N'-dimethylbarbituric acids?arylidene Meldrum acids?in dry methylene dichloride at room temperature afforded 7,9-diazaspiro[4.5]dec-l-enes and 7,9-dioxaspiro[4.5]dec-l-enes in good yields and with high diastereoselectivity.All the new products were characterized by IR,¹H NMR,¹³C NMR and HRMS spectroscopy.The single structure of five compounds were determined by X-ray diffiraction method.When dimethyl acetylenedicarboxylate was used in the three-component reaction,the 5-?triphenyl-15-phosphanylidene?cyclopenta-1,3-dienes wereobtai-ned in moderate yields.The experimental results showed that dimethyl hex-2-en-4-ynedioate resulted in 7,9-diazaspiro[4.5]dec-l-enes.On other hand hand,the reaction with dimethyl acetylenedicarboxylate gave the substituted cyclopentane derivatives.The three-component reaction of triphenylphosphine,dialkyl azodicarboxylates,and 3-phenacylidenoxindoles afforded ethyl??E?-3-??Z?-2-??ethoxycarbonyl?imino?-2-phenylethyli-dene?-2-oxoindolin-4-yl?carbamate in good yields and with high diastereoselectivity.All the new products were characterized by IR,¹H NMR,¹³C NMR and HRMS spectroscopy.The single structure of one compounds were determined by X-ray diffiraction method.The experimental results indicated the reaction has a widely variety of substrates and is the efficient synthetic protocol for oxindole substituted urethane derivatives.