Catalytic Asymmetric 1,3-Dipolar Cycloaddition of α,β-Unsaturated Amide and Azomethine Imine Zhao Li.pdf

该【Catalytic Asymmetric 1,3-Dipolar Cycloaddition of α,β-Unsaturated Amide and Azomethine Imine Zhao Li 】是由【tiros009】上传分享，文档一共【3】页，该文档可以免费在线阅读，需要了解更多关于【Catalytic Asymmetric 1,3-Dipolar Cycloaddition of α,β-Unsaturated Amide and Azomethine Imine Zhao Li 】的内容，可以使用淘豆网的站内搜索功能，选择自己适合的文档，以下文字是截取该文章内的部分文字，如需要获得完整电子版，请下载此文档到您的设备，方便您编辑和打印。←確認用doi(左上Y座標:-),552–554(2020),,3-DipolarCycloadditionofα,β-UnsaturatedAmideandAzomethineImineZhaoLi,NaoyaKumagai,*andMasakatsuShibasaki*InstituteofMicrobialChemistry;3–14–23Kamiosaki,Shingawa-ku,Tokyo141–0021,,2020;acceptedMarch10,2020α,β-Unsaturatedamideswereincorporatedasviabledipolarophilesinacatalyticasymmetric1,3--azaindolineauxiliarywasessentialtoacquiresu?cientreactivitywithexcellentdiastereoselectivity,likelyduetothechelatingactivationoftheamidebytheIn(III)/,thisworkisanimpor-atalysisutilizingstableandlow-,3-dipolarcycloaddition;indium;7-azaindoline;amide;enantioselectiveIntroductiontivitywaslargelydeterminedbysubstratesandremaineduni-monstructuralsubsetsinaformly?high.?Unexpectedly,?BHA-1,3,optimalBHAligandsinpounds,suchasagro-thereactionwith2aandnitrones,44)–4)1,3-es.?Structural?modi?cations?to?increase?or?decrease?the?reactions?o?er?expeditious?construction?of?heterocycles?by?stericfactor(BHA-2,4)marginallyimprovedboththeyieldofingtwobondsinanintermolecularman-3a?and?enantioselectivity.?Ligand-bearing??uorene?substituents?–9)Azomethineimine1derivedfrom3-pyrazolidinone(BHA-5)?a?orded?higher?yields?but?the?enantioselectivity?,11)?The??rst?disclosure?of?cata-(BHA-6)improvedtheenantioselectivity(45%enantiomericlyticasymmetric1,3-dipolarcycloadditionof1wasreportedexcess?(ee)).?BHA-7,8,inwhichthemethyleneunitswerebyFuandcolleagues,inwhich1andterminalalkynesweretruncatedtoinducemorestericbias,deliveredalmostrace-enantioselectivelycoupledbytheactionofachiralCu(I)micproduct3a?in?excellent?yield.?An?aliphatic?BHA?ligand?complex?and?an?,13)Thisinitialdiscoverywasfol-armedwithadamantlygroups(BHA-9)?exhibited?poor?cata-lowed?by?1,3-dipolar?cycloadditions?using?electron-de?cient??ns?as?dipolarophiles,?a?ording?a?series?of?enantioenriched?optimalligandBHA-)The7-azaindolineproducts?with?the?expected?regioselectivity?(N1–Cb)14–32)auxiliary?proved?indispensable?for?acquiring?su?cient?reactiv-(Chart1).Bytakingadvantageoftheiminiumcharacterofitywithazomethineimine1(Chart2).Structurallysimilar1,?electron-rich?ole?ns,?including?enolate?species,?can?reverse?indolineamide2bor5-azaindolineamide2cwasunreactivetheregioselectivity,onditions(2b,c),indicatingthatpoundswiththeN––42)Forthereac-chelatingcoordinationofthe7-azaindolineamidemoiety(2a)tion?with?electron-poor?dipolarophiles,?electron?de?ciency?is?a?)Intriguingly,anprimarydeterminantthatcontrolsthereactivity,andtherebyacyclicamide(2d)capableofchelationviaapyridylnitrogenthescopeofdipolarophileshasbeenlargelylimitedtohighlyfailedinthereaction,implyingtheuniquenessofthecyclicelectrophilic?ole?ns?conjugated?with?aldehyde,14,18)ketone,15,26)7-azaindoline?auxiliary?for?strong?activation.?As?expected,?imide,16,17)?oxindole,21,25),24)Inourcontinuing?e?orts?to?engage?less?electrophilic?α,β-unsaturatedamidesincatalyticasymmetricreactions,43–45)wereasonedthat?our?7-azaindoline?auxiliary?allows?for?1,3-dipolar?cycload-ditionof1?with?less?reactive?amide-conjugated?ole?ns.?Herein?wereporttheincorporationofα,β-unsaturatedamidesasaviabledipolarophileinthe1,3-dipolarcycloadditionofazome-,3-dipolarcycloadditionofα,β-unsaturated7-azaindolineamides2promotedbytheIn(III)/bishydroxamic?acid?(BHA)46–54)catalyticsystem,44)we?began?our?investigation?by?screening?the?BHA?sca?old?in?thereactionusingazomethineimine1(Table1).Intriguingly,bothchemicalyieldandenantioselectivitychangeddrasticallydependingontheBHAligandused,whilethediastereoselec-*?Towhomcorrespondenceshouldbeaddressed.?e-mail:******@;******@?,(2020))a)1:,2a:(dr)wasdeterminedby1H-NMR?analysis?of?the?crude?mixture.?Enantioselectivity?(ee)?was?determined?by?chiral?),3-DipolarCycloadditionofVariousα,β-UnsaturatedAmidesasimpledimethylamide(2e)wasunreactive,whichfurtherhighlightstheutilityof7-,weinvestigatedthescopeofthepresent1,3-dipolarcycloadditionofα,β-unsaturated7-azaindolineamides2(Table2).Reactioncouldberunwithlower?catalyst?loading?(5?mol%)?to?a?ord?-phenylgroupatm-andp-positionswastoleratedtogiveproduct3f,-withdrawingsubstitu-entsatthepara-patible,albeitwithslightlydiminishedenantioselectivity(3h–j).Thehighreactivitywasmaintainedwithamideshavingelectron-donatingfunction-alities(p-OTBS,p-OMe,m-OMe),deliveringproduct3k–mwithhigherenantioselectivitythantheproducts3h–jwithelectron-,wedevelopedacatalyticasymmetric1,3-dipolarcycloadditionofanazomethineimineincorporat-a)1:,2:(dr)1ingα,β--NMR?analysis?of?the?crude?mixture.?Enantioselectivity?(ee)?-,(2020)theticpointofview,mun.,50,10218–10221(2014).developingcatalyticasymmetricreactionsutilizinggenerally25)?Yin?C.,?Lin?L.,?Zhang?D.,?Feng?J.,?Liu?X.,?Feng?X.,?.Chem.,unreactiveα,β-,9691–9699(2015).26)GongJ.,WanQ.,KangQ.,.,20,3354–3357(2018).27)?For?the?construction?of?larger?ring?systems?using?more?conjugated?AcknowledgmentsThis?work?was??nancially?supported?substrates,?see:?Du?Q.,?Neudor??J.-M.,?Schmalz?H.-G.,??KAKENHI?(17H03025?and?18H04276?in?Precisely?De-J.,24,2379–2383(2018).signed?Catalysts?with?Customized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