金沢大学大学院自然科学研究科生理活性物質科学金沢大学薬学部A lithium hydroxide promoted glucosidation of 1-hydroxyindoles with 2, 3, 4, 6-tetra-0-acetyl-α-D-glucopyranosyl bromide is newly developed. Applying this method, the first and simple syntheses of novel indol-1-yl glucosides were achieved

Hayashi Toshikatsu

Somei Masanori

Yamada Fumio

Yamada Koji

Kanazawa University Repository for Academic Resources

Simple syntheses of indol-1-yl glucosides著者 Yamada Fumio, Hayashi Toshikatsu, Yamada Koji,Somei Masanorijournal orpublication titleHeterocyclesvolume 53number 9page range 1881-1884year 2000-09-01URL http://hdl.handle.net/2297/43621８８１ HETEROCYCLES,Ｖｏ１．５３，No.９，２０００ ＳＩＭＰＩＥＳＹＮＴＨＥＳＥＳＯＦＩＮＤＯしl－ＹＬＧＬＵＣＯＳＩＤＥＳ１IhlmioYamada,TbshikatsuHayashi,KQjiYamada,andMasanoriSomci＊ FbucultyofPharmaccuticalScicncＣｓ,KanazawaUmvcrsity， 13-1Tnkara-machi,Kanazawa920-0934,Japan Abmzuct-Ahthiumhydroxidcpromotcdglucosidationofl-hydroxyindolcs with２，３，４，６－tetra-O-acctyl-a-D-glucopyranosylbromidcisncwlydcvclopcd・Applyingthismcthod，thcfirstandsimplcsynthcscsofnovclindol-1-yl gducosidcswcrcachicvcd． Varictyofglycosidcsandnuclcosidcsarcwidclydistributcdinnaturcandthcyplayimportantrolesm Uvingorganisn1s､２１nourl-hydroxymdolchypothcscs,３awespcculatcdthccxistcnccandro】csofanovcltypcofcompounds,indol-1-ylglycosidcs(1,2,etc.)asshownmgcncralfbrmulacinFigurcLA1though manyglucosidationmcthodshavcbccnrcportcd,４wchavcnotbccnablctoobtainsatisfactoryrcsultsin applyingthcm5tol-hydroxymdolcswithanhopctoproducclNow，wcwishtorcportthcsucccssm dcvclopinganovclsynthcticmcthodwcll-suitcdfOrthcprcparationofl・Amongvariousl-hydroxyindolcs，l-hydroxyWb-mcthoxycarbonyltryptaminc（3a)，apotcntplatclct aggrcgationmhibitor,６wassclcctcdasasubstratefOrcxaminingglucosidationwith2,3,4,6-tctra-O‐ acctyl-a-D-glucopyranosylbromidc7(4)asshowninSchcmcLSinccl-hydroxyindolcsarewcak acids,3bthcrcactionwascarriedoutinthcprcscnccofbase,andthcglucosidatcdproductswcrcisolatcd aftcracctylationwithAc20andpyridincinordcrtofacilitatcseparation・Typicalproccdurcisasfbllows・Initially，３awasdissolvcdinamcthanolsolutioncontainmganappropriatcbasc(6molcq.)andthcsolvcntwasevaporatcdundcrrcduccdprcssurctodryncss・Tothcrcsultantmctalsaltof3awasaddcdasolutionof4(3molcq.)inDMFandaUowcdtorcactatroom tcmpcraturcfbr4hAftcrusualworkup，thcproductswcrcacctylatcdwithAc20andpyridincatroom tcmpcraturｃｔｏｇｉｖｅ５ａａｎｄ６ａ、ItwasfOundthatDMFisthcsolventofchoiccamongthccxaInincdMcOH,Ｅｔ２ＱＴＨＦ,ａｎｄＤＭＦ,and thcyicldof5adcpcndsonbascs・Thus,whcnCs2CO3wasuscd,５aand6awcrcgcncratcdinl5and65％yiclds，respcctivcly・ＥｍｐｌｏｙｍｇＣｓＯＨＨ２０,ｔｈｃｙｉｃｌｄｏｆ５ａｗａｓｒａｉｓｃｄｔｏ２４％togcthcrwith30％ｙｉｃｌｄｏｆ６ａ・Slightincrcascinthcyicldof5ato２８％ｗａｓｏｂscrveduponuscofKOHinadditionto３７％yicldof6a、ＩｎｔｈｃｃａｓｃｏｆＮａＯＨ，Ｓａａｎｄ６ａｗｃｒｃｐｒｏｄｕｃｃｄｉｎ４３ａｎｄ５２％yiclds，rcspcctivcly・Dramaticalimprovcmcntintheyielｄｏｆ５ａｕｐｔｏ９３９Ｍｒａｂｌｃｌ,Ｅｎｔｒｙｌ）wasfinallyachicvcdupon cmploymgljOHasthcbascthoughfbnnationof6awasobscrvcdin６％yicld,mc6-configulationof5a wasprovcdbythccouplingconstantofthcanomcricproton(に8.1Ｈｚ)whichisrcadilydisccrniblcmthcNMRspcctrumofindol-1-ylβ-D-glucopyranosidc(7)obtaincdin84％yicldbyhydrolysisof5awith NaOMcｉｎＭｅＯＨ・Undcrthcsamcrcactionconditions，thcLiOHpromotcdreactionwassucccssfUUyappUcdtoothcrbiolog‐ 1８８２ HETEROCYCLES,Ｖｏ1.53,No.9,2000 Figurel Ｙ,Ｚ＝anappropriate substituent .Ⅶ労０ 孫謡㈱･’○〔pHfl5sご=i二/ＡＨＯ PepUde ptide Ｃ ＮノＨＮ－ｐｅＯＨ H85s~≦/８㈹85s邑二､≦/８ Ｈ Ｂ ２ ７ Schemel 幽繊<』AcO A9Rn=ニミミＡｃＯＢｒ ｏ＋Ｒ－ＯＡｃ ＲＯＨ ＋ ＡＣＯ 2)ＡＣ20,pyridina rt,３ｈ (３moleq.） ⑥ 5 ３ ４ Table1.ReactionofHydroxyCompound(3)with2,3,4,6-Tetra-O-acetyl-aD-gluco‐ pyranosylBromide(４１)inthePresenceofLiOHFollowedbyAcetyIationwith Ac20andPyridine YieldG6） ｏｆＳ R－ＯＨ ３ Ｒ－ＯＨ ３ Yield(％） ｏｆら Entry Entry 騨酬函鍼如駕､ＩＨＯ＜_>Ｃ 9３ ｌａ ｇ圏NＣ7ｓ ２ｂ ○ ｇＨ。｛>NＣＳｃ 77 ＯＨ icallyactivcl-hydroxyindolcs・Mcthyll-hydroxyindolc-3-butylatc6(3b)andl-hydroxymclatonin(3c）affOrdcd5band5cin78and77％yiclds,rcspcctivcly(Entrics2,3）Whcnthcrcactionwasapplicdto HETEROCYCLES,Ｖｏｌ､53,No.９，２０００ 1８８３ P-mcthoxyphcnol(3.),thcyicldofthccxpcctcdglucosidc(5.)8was５４％(Entry4).Onthcothcrhand， morcacidicl-hydroxy-5-nitroindolc(3e)，８－oxyquinolinc(3f)，andp-nitrophcnol(39）affbrdcdthc corrcspondingglucosides,(5e'５f,ａｎｄ５ｇ９),in42,35,and29％yiclds,respcctivcly(Entries5-7)． ApplicationofthcsefactMolhcfirstsynthcsisofcapparilosidcsA1O(8)wassucccssfUUycarricdoutas reportedinthcprcviouspapcr､n ThcscdataclcarlysuggcstthatthｉｓＬｉＯＨｐｒｏｍｏｔｃｄｒｃａｃｔｉｏｎｉｓｐＫＺｕｄｃpcndentanditsccmstogivc sufficicntrcsultsfbrthchydroxycompoundshavingpKZJvalucsof8-103b lnconclusion，wchavcdevclopcdanovclmcthodwhichissuitablcfbrthcsynthescsofglucosidesof l-hydroxyindolcs・Astudyfbrinvcstigatingthcirchcmicalreactiviticsandbiologicalevaluations，andfUrthcrcxtcnsiontovariousglycosidcssynthcscsarccurrcntlyi､progress． ＲＥＦＥＲＥＮＣＥＳＡＮＤＮＯＴＥＳ １・ThisisPartlO1ofascricscntiUcd“nleChcmistryoflndolcs”・PartlOO:Ｍ・Somci，YFukui,Ｍ、Hascgawa，Ｎ・Oshikiri，ａｎｄＴ，Hayashi,Ｈｅに、ｑﾉcﾉｾs，２０００，５３，１７２５．AllncwcompoundsgavCsatisfactoryspcctralandclcmcntalanalysisorhigh-rcsolutionMSdatafbrcrystalsoroils,rcspcctivclV、５acolorlcssoil,[α]D24-8.4｡(c=0.25,McOH);5b,mp88-89℃(EtOH),[α]D28-242｡(c=0.43, CHCl3);Ｓｃ,ｍｐｌ３８－１４０°Ｃ(McOH),［cqD27-22.2｡(←0.28,CHC13);５e,ｍｐ２１１－２１２°Ｃ （McOH),［α]D26-38.2｡(c=0.34,CHCl3);５ｆｍｐｌ６６－１６８ｏＣ(EtOH),［α]D26-57.7｡(c=0.24, CHCl3);7,colorlcssoil,[qlD274Z5｡(c=0.21,McOH)． ２．ｓ.Ｈ、Ｐinc,OrganicChemistry,McGraw-HillBookCo.,ＮｅｗＹｏｒｋ,1987.3．ａ)Ｒｅｖｉｅｗ:Ｍ､Somei,比ZeroCyclbs,1999,50,1157andrcfCrcnccscitcdthcrcin.b)ThcpKZJvalucsofcompounds:(±)JVb-acctyl-1-hydroxytryprophanmcthylcstcr,９８;３b,8.4;3.,10.2;３e,6.8;３f， ４．９９，３９，６９． ４．ａ)ＥＭ･MOntgomcry,ＮＫ・Richtmycr,andCSHudson,ＪＡ腕.CAe"z・ＳＯＣ，1942,Ｍ,691;ｂ）RRSchmidtandJ・Michel,Ａ"gew・die"L，1980,92,763;c)HPaulscn,Ａ"gcwOie，".,1982,04,184;。)Ｒ､Ｒ､Schmidt,Ａ"gcwCﾉbe"2.,mK肌肋81,1986,25,212;ｃ)KSuzukiandT、Nagasawa,ＪＪｙ"’2.0'９Ｃｈｅｿ?2．（JZW,”，1992,50,378;f)KToshimaandK､Tatsuta,diel?z・Rev.，1993,93,1503. 5．Dirccthcatingof3a-cwithq-D-glucoscandusualacidcatalyzcdacctalcxchangcrcaction4ofpcnta‐ Oacctyl-q-D-glucopyranosidc4awith3a-cdidnotaffOrdthccxpcctcdglucosides(5a-c)Rcactionsnf ３a-cwith4usingBu4N+ＨＳＯ４－ｉｎａｑ、ＮａＯＨ－ＣＨＣ１３９ｂｗａｓｎｏｔｓｕcccssfUlRcactionsof3m-cwith2,3,4,6-tetra-0acctyl-a-D-glucopyranosyltrichloroacctimidatc4bundcracidicconditionsrcsultcd inthcfbrmationsoftars、６．Ｍ．Somei，Ｋ・Yamada，MHascgawa，MTHbata，Ｙ・Nagahama，Ｈ・Morikawa，ａｎｄＦＹａmada，HbZeroCycに8,1996,43,1855.7.Ｍ.Bdrczai-MartosandF・Kor6sy,MuZz"9e，１９５０，１６５，３６９．８．ＥＲ・Novik，VMSokolov，ＥＰ、Studentsov，Ｖ、１．Zakharov，ａｎｄＡＮ・Lavrcnticv，ＪＢＯ印．Ｃ/be、.，ＵＳＳＲ，１９８６，５０，１５９;Ｆ、C1crici，ＭＬＧｃｈｉ，andSMOttadclU,エＣﾉie"@．ＳＯＣ，化成mTrzms､１，１９９４，９８５;ＴＭ・S1aghck,YNakahara，Ｔ、Ogawa,Ｊ・Ｐ・KamcrUng,ａｎｄＪＦ．Ｏ．1８８４ HETEROCYCLES,Ｖｏｌ､53,No.9,2000 Ⅵiegcnthart,ＣＭ)oﾉｶy‘.比s・'1994,255,61.9．ａ)Ｔ・IvcrscnandR・Johansson,Sy"伽sjs,1979,823;b)Ｄ・Dcss,HPK1einc,，.Ｖ・Wcinbcrg,RJKaufinan,ａｎｄＲ､SSidhu,肋jZjL，1981,883;c)MYamaguchi,AHoriguchi,AFnkuda,andTMinami,Ｊ､Ｃｈｅ腕.ＳＯＣ.,Ｐﾋﾞｸﾞ肋zTrzJ"８．Ｊ，1990,1079.10.LCalis,AKumiiziim,andPRiicdi,Ｐｈ)'ｍｃｈ伽Ｓｍ1,1999,50,1205.lLMSomciandFYamada,HbZcroCycに8,2000,53,1573.Received，２１ｓｔｊｕｎｅ，２０００ 

Simple syntheses of indol-1-yl glucosides

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Simple syntheses of indol-1-yl glucosides

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