Catalytic Cycloisomerization onto a Carbonyl Oxygen - Shi et al. - Unknown - Unknown

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CatalyticCycloisomerizationontoaCarbonylOxygenShichengShi,†JonathanL.Kuo,†TaoChen†andJackR.Norton*,††DepartmentofChemistry,ColumbiaUniversity,3000Broadway,NewYork,NewYork10027,UnitedStatesjrn11@columbia.eduSupplementaryInformationTableofContents1ExperimentalProceduresandCharacterizationData2•ReactionOptimization2•PreparationofStartingMaterials8•CycloisomerizationunderCobaloxime/H2condition17•Cycloisomerizationundersalen-Co(III)/silanecondition22•MechanisticStudies31References331Hand13CNMRSpectra34CorrespondingAuthor:Prof.Dr.J.NortonDepartmentofChemistryColumbiaUniversity,3000BroadwayNewYork,NewYork10027,UnitedStatesE-mail:jrn11@columbia.edu

1Allstartingmaterialsreportedinthemanuscripthavebeenpreviouslydescribedinliteratureorpreparedbythemethodreportedpreviously.1-7Allexperimentsinvolvingcyclizationreactionwereperformedunderargoningloveboxunlessstatedotherwise.AllsolventswerepurchasedatthehighestcommercialgradeandusedasreceivedorafterpurificationbypassingthroughactivatedaluminacolumnsordistillationfromNa/benzophenoneundernitrogen.Allsolventsweredeoxygenatedpriortouse.Allotherchemicalswerepurchasedatthehighestcommercialgradeandusedasreceived.Reactionglasswarewasoven-driedat140°Cforatleast24horflame-driedpriortouse,allowedtocoolundervacuum.Allproductswereidentifiedusing1HNMR,13CNMRand/orHR-MSanalysis.Allyieldsrefertoyieldsdeterminedby1HNMRusinganinternalstandard(nitromethane)unlessstatedotherwise.1HNMRand13CNMRspectrawererecordedinCDCl3,CD2Cl2andAcetone-d6onBruker500Ascend,DRX500corDRX400spectrometer.Allcouplingconstants(J)arereportedinhertz(Hz).Abbreviationsare:s,singlet;d,doublet;t,triplet;q,quartet;brs,broadsinglet.High-resolutionmassspectra(HRMS)weremeasuredona7TBrukerDaltonicsFT-MSinstrumentbyelectrosprayionization(ESI)probe.Allflashchromatographywasperformedusingsilicagel,60Å,300mesh.TLCanalysiswascarriedoutonglassplatescoatedwithsilicagel60F254,0.2mmthickness.Theplateswerevisualizedusinga254nmultravioletlamporaqueouspotassiumpermanganatesolutions.1HNMR,13CNMRandHRMSdataaregivenforallcompoundsintheSupportingExperimentalforcharacterizationpurposes.1HNMR,13CNMRandHRMSdataarereportedforallnewcompounds.Deuteratedbenzene(C6D6)wasdistilledfrommoltenpotassium&benzophenoneketyl.Benzene(C6D6)andtetrahydrofuran(THF)weredistilledfromsodium-benzophenoneketyl.CpCr(CO)3H,andCo(dmgBF2)2(THF)2weresynthesizedaccordingtotheliteratureprocedures1-2andstoredinanargonatmosphereglovebox(O2<1ppm).DetailedOptimizationExperimentsGeneralProcedure:ThecobaltorchromiumcatalystsandN-vinylindole1(0.2mmol)wereweighedinaglassvialandtransferredtoaFisher-Portertubeequippedwithamagneticstir-barusing4mLofdryanddegassedbenzene.Thetubewasthenplacedbehindanappropriateblastshieldbeforeitwaspressurizedto2.0atmofH2.Thevesselwasthenimmediatelyventedandrepressurizedandthisoperationwasrepeatedtwentytimes,topushouttheinertatmosphere.TheSI-2

2vesselwaspressurizedto2.0atmofH2for30seconds.Ifnochangeinpressurewasobserved,thetubewaspressurizedto4.8atmor6.0atmofH2,andstirredat60ºCor90ºCfor3days.(NOTE:ThepressurizedFisher-Portertubeshouldalwaysbeplacedbehindanappropriateblastshield!!!)Aftertheindicatedtime,theFisher-Pottertubewascooledtoroomtemperature,H2gaswasventedslowly,thentheFisher-Portertubewasdisassembled.Thecrudereactionmixturewasfilteredthroughashortsilicagelplug,andtheplugwaswashedwithethylacetate.Theresultingfiltratewasconcentratedandthecrudereactionmixturewasanalysedby1HNMR(CDCl3,CD2Cl2,C6D6orCD3C(O)CD3)todetermineproductdistributionandselectivitywithinternalstandard.TableS1.InitialOptimizationStudiesUnderCobaloxime/H2aSI-3

3aConditions:1d(0.2mmol),7.0mol%C-1,4.8atmHob2,benzene(0.05M),50C,threedays.Determinedby1HNMRwithinternalstandard.c20mol%C-1wasused.dunder6.1atmHe2.underArwithoutH2.OptimizationStudiesWithCo(III)-salen/silaneGeneralProcedure:Intheglovebox,toanoven-dried6mLvialequippedwithastirbarwasAddedtheindolesubstrates1(0.1mmol)andCo(III)-salen(6mol%or12mol%).Thiswasfollowedbytheadditionofastocksolutionofsilane(6mol%or12mol%)(1.0mL).Thevialwassealedwithawhitecap,andfurthersealedusingblacktape.Thereactionmixturewasremovedfromglovebox,putinpre-heatedoilbath(60oCorindicatedtemperature)for16h.Aftertheindicatedtime,thereactionmixturewascooleddowntoroomtemperature,filteredthroughashortplugofsilicagel,andelutedwithEtOAc.Theresultingfiltratewasconcentratedandthecrudereactionmixturewasanalysedby1HNMR(CDCl3,CD2Cl2orCD3C(O)CD3)todetermineproductdistributionandselectivity.Ratioisreferredtocycloisomerization(2)/isomerization(3).FigureS1.StructureofCo(III)-salenusedforoptimizationTheCo(III)-salencomplexesA-Iwerepreparedaccordingtoknownprocedures.3,4SilanewasusedasastocksolutioninBenzene.SI-4

4TableS2Investigationofthetemperatureandconcentration:aEntryTemperatureConcentrationConv.b(%)Ratioof2d:3db123oC0.1M10>20:1240oC0.1M456.7:1360oC0.1M804.5:1480oC0.1M>952.1:1560oC0.01M783.5:1660oC0.5M753.3:1aConditions:1d(0.1mmol),6.0mol%A,12mol%PhSiHb13,benzene,temperature,16h.DeterminedbyHNMRwithinternalstandard.TableS3.Investigationofsilaneasreductant:aEntrySilaneConv.b(%)Ratioof2d:3db1Et3SiH10>20:12(EtO)3SiH456.7:13Ph3SiH804.5:14PHMS333.1:15PhSiMeH2282.6:16Ph2SiH2786.5:17PhSiH3804.5:1SI-5

5aConditions:1d(0.1mmol),6.0mol%A,12mol%silane,benzene(0.1M),60oC,16h.bConversionandratioof2d:3ddeterminedby1HNMRwithinternalstandard.TableS4.Investigationofsalen-Co(III)-Xcatalyst:aEntrySalen-Co(III)Conv.b(%)Ratioof2d:3db1A916.5:12B909.2:13cB>958.5:14C896.0:15D353.4:16E214.5:17F372.4:18G433.2:19H5112:110dH904.2:111I942.3:1aConditions:1d(0.1mmol),6.0mol%salen-Co(III),12mol%Pho2SiH2,benzene(0.1M),60C,16h.bConversionandratioof2d:3ddeterminedby1HNMRwithinternalstandard.c12.0mol%Bwasused.cunder80oCTableS5Investigationofringsizeoftetheredcyclicketones:aSI-6

6EntrynConv.b(%)Ratioof2:3b1567<1:6726801.7:137947.6:148958.5:159943.3:1aConditions:1(0.2mmol),12.0mol%B,12mol%Phob2SiH2,benzene(0.1M),60C,16h.Conversionandratioof2:3determinedby1HNMRwithinternalstandard.SI-7

7PreparationofStartingMaterialsS1-S2,S3-S5werepreparedaccordingtoreportedprocedures.5,6GeneralprocedureforpreparationofS1andS2:5Enamine(5.0mmol)wasaddedto5mLdioxaneina20mLovendriedRBF,then2,3-dibromoprop-1-ene(0.55mL,0.55mmol)wasaddeddropwise,thereactionmixturewasstirredatrefluxfor3hours.Thereactionmixturewasthencooledtoroomtemperature,followedbyadditionof1NHCl(1mL).Thereactionwasheatedatrefluxforadditional1hour,TLCindicatedthedisappearanceofthestartingmaterial.Solventwasremovedinvacuo,andtheproductwaspurifiedviachromatography(hexane/EtOAc=50:1-10:1)affordthefinalproductascolourlessoil.(stainedwithaqueouspotassiumpermanganatesolutions)2-(2-Bromoallyl)cyclopentan-1-one(S1):5.0mmolscale,theproductwaspurifiedthroughchromatography(hexane/EtOAc=50:1-10:1)affordascolourlessoil.Yield80%(804mg).1HNMR(400MHz,CDCl3)δ5.62(td,J=1.6,0.7Hz,1H),5.44(dd,J=1.7,0.7Hz,1H),2.95(dd,J=15.0,4.0Hz,1H),2.54–2.21(m,4H),2.15(ddd,J=18.8,10.4,8.8Hz,1H),2.03(dddt,J=13.6,9.0,6.8,2.4Hz,1H),1.91–1.76(m,1H),1.51(dtd,J=12.8,11.0,6.8Hz,1H).Spectrumdatamatchwithpreviouslyreported.2-(2-Bromoallyl)cyclohexan-1-one(S2):5.0mmolscale,theproductwaspurifiedthroughchromatography(hexane/EtOAc=50:1-10:1)affordascolourlessoil.Yield78%(842mg).1HNMR(400MHz,CDCl3)δ5.60(td,J=SI-8

81.6,0.8Hz,1H),5.44(dd,J=1.6,0.8Hz,1H),3.00(dd,J=14.8,4.2Hz,1H),2.76–2.63(m,1H),2.48–2.31(m,2H),2.27(dd,J=14.8,9.0Hz,1H),2.18(ddt,J=11.7,5.9,3.0Hz,1H),2.10(ddt,J=12.3,6.3,3.0Hz,1H),1.94–1.85(m,1H),1.78–1.58(m,2H),1.31–1.17(m,1H).Spectrumdatamatchwithpreviouslyreported.GeneralprocedureforpreparationofS3-S5:6ToasolutionoffreshpreparedLDA(5.5mmol,1.1equiv),asolutionofcorrespondingcyclicketone(5.0mmol,1.0equiv)inTHF(3.0mL)wasaddeddropwiseat0oC.Thereactionwaswarmedtoroomtemperatureandstirredfor30min.Then2,3-dibromoprop-1-ene(0.55mL,0.55mmol)wasaddedthereactionwasstirredatroomtemperaturefor15hours.ThereactionwasquenchedbyNH4Cl(10mL)andextractedwithEt2O(3x15mL);thecombinedorganiclayerwasfurtherwashedwithbrine(20mL)anddriedoverNa2SO4.Thesolventwasremoved,andtheproductwaspurifiedthroughchromatography(hexane/EtOAc=50:1-10:1)affordthefinalproductascolourlessoil.(stainedwithaqueouspotassiumpermanganatesolutions)2-(2-Bromoallyl)cycloheptan-1-one(S3):5.0mmolscale,theproductwaspurifiedthroughchromatography(hexane/EtOAc=50:1-10:1)affordtheascolourlessoil.Yield82%(947mg).1HNMR(400MHz,CDCl3)δ5.60(dd,J=1.8,0.9Hz,1H),5.45(dd,J=1.6,0.7Hz,1H),2.96(dddd,J=10.1,8.4,5.6,3.0Hz,1H),2.91–2.81(m,1H),2.58(dddd,J=15.6,5.3,4.3,1.2Hz,1H),2.45(ddd,J=15.5,11.0,4.3Hz,1H),2.37(ddd,J=14.7,8.3,0.8Hz,1H),1.92–1.79(m,4H),1.78–1.66(m,1H),1.56–1.45(m,1H),1.39–1.23(m,2H).13CNMR(101MHz,CDCl3)δ214.2,132.6,49.6,43.5,42.9,29.9,29.3,29.0,23.9.HRMS(ESI)m/z:[M+Na]+CalcdforC10H15BrONa230.0305,found396.1791.2-(2-Bromoallyl)cyclooctan-1-one(S4):30.0mmolscale,theproductwaspurifiedthroughchromatography(hexane/EtOAc=50:1-10:1)affordascolourlessoil.Yield75%(5.59g).1HNMR(400MHz,CDCl3)δ5.59–5.55SI-9

9(m,1H),5.41(d,J=1.7Hz,1H),3.14(dtd,J=10.4,7.1,3.6Hz,1H),2.82(ddd,J=14.4,7.4,1.1Hz,1H),2.49(ddd,J=14.2,7.8,3.2Hz,1H),2.40(ddd,J=14.4,6.7,1.0Hz,1H),2.32(ddd,J=14.1,10.9,3.2Hz,1H),2.10(dddd,J=17.6,10.9,5.4,3.3Hz,1H),1.90(ddt,J=13.7,7.1,3.4Hz,1H),1.85–1.75(m,1H),1.72–1.55(m,5H),1.49–1.37(m,1H),1.19–1.06(m,1H).13CNMR(101MHz,CDCl3)δ218.2,132.1,119.0,47.6,43.5,43.3,32.5,28.0,25.0,24.9,24.6.HRMS(ESI)m/z:[M+H]+CalcdforC11H18BrO245.0541,found245.0547.2-(2-bromoallyl)cyclododecan-1-one:5.0mmolscale,theproductwaspurifiedthroughchromatography(hexane/EtOAc=50:1-10:1)affordascolourlessoil.Yield66%(990mg).1HNMR(400MHz,CDCl3)δ5.61–5.59(m,1H),5.43(d,J=1.7Hz,1H),3.07(p,J=6.5Hz,1H),2.80(ddd,J=17.0,9.9,3.2Hz,1H),2.72(dd,J=14.6,7.2Hz,1H),2.45(dd,J=14.7,7.3Hz,1H),2.28(ddd,J=17.0,7.6,3.5Hz,1H),1.88(tq,J=10.3,4.5,3.3Hz,1H),1.67(q,J=7.6Hz,2H),1.34–1.25(m,15H).13CNMR(101MHz,CDCl3)δ213.1,132.2,118.9,49.1,42.2,38.8,28.5,26.2,25.9,24.2,23.9,23.7,22.4,22.0,21.9.HRMS(ESI)m/z:[M+H]+CalcdforC15H26BrO301.1167,found301.1172.Generalprocedureforpreparationof1a-1p:5Toa20mLpressuretubewasaddedthesubsituted-indole(5.5mmol)andthenK3PO4(2.12g,5.0mmol),CuI(95.0mg,0.5mmol),5mLofdegasseddioxane,andethane-1,2-diamine(0.06mL,1.0mmol).Thiswasfollowedbytheadditionofvinyl-bromide(1.0mmol)inoneportion.ThepressuretubewassealedwithaPTFEplug,andthemixturewasheatedat110°Cfor24h.Themixturewascooledtoroomtemperature,andethylacetate(20mL)wasaddedfollowedbyfiltrationthroughashortplugofCelite.Theorganicphasewasconcentratedunderreducedpressure,andtheresultingresiduewaspurifiedbycolumn(toluene/DCM50:1-10:1)toyieldthetitledcompound1asacolorlessoil.SI-10

102-(2-(1H-indol-1-yl)allyl)cyclopentan-1-one(1b):5.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-10:1)affordascolourlessoil.Yield57%(681mg).1HNMR(400MHz,CD3C(O)CD3)δ7.64–7.53(m,2H),7.39(d,J=3.3Hz,1H),7.19(ddd,J=8.5,7.1,1.2Hz,1H),7.07(ddd,J=7.8,7.1,1.1Hz,1H),6.57(dd,J=3.4,0.7Hz,1H),5.34–5.27(m,1H),5.20(s,1H),3.21(ddd,J=15.1,3.8,1.3Hz,1H),2.46(dd,J=15.1,9.8Hz,1H),2.17(dddt,J=18.3,8.2,2.6,1.6Hz,1H),2.04–1.86(m,4H),1.71–1.52(m,2H).13CNMR(101MHz,CD3C(O)CD3)δ218.6,144.4,136.7,130.2,127.5,122.9,121.6,120.9,112.0,108.5,103.8,47.4,37.9,36.4,20.9.Spectrumdatamatchwithwhatwaspreviouslyreported.72-(2-(1H-indol-1-yl)allyl)cyclohexan-1-one(1a):5.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-10:1)affordascolourlessoil.Yield53%(670mg).1HNMR(400MHz,CD3C(O)CD3)δ7.61–7.54(m,2H),7.36(d,J=3.3Hz,1H),7.17(ddd,J=8.4,7.0,1.2Hz,1H),7.07(ddd,J=7.9,7.0,1.0Hz,1H),6.56(dd,J=3.3,0.8Hz,1H),5.24(d,J=0.7Hz,1H),5.20(s,1H),3.29(ddd,J=15.2,4.7,1.3Hz,1H),2.40(dd,J=15.3,8.8Hz,1H),2.35–2.23(m,3H),2.14(ddq,J=12.4,5.7,3.3Hz,1H),2.02–1.94(m,1H),1.77(ddd,J=11.5,4.4,2.3Hz,1H),1.65–1.45(m,2H),1.36(qd,J=12.4,3.6Hz,1H).HRMS(ESI)m/z:[M+H]+CalcdforC18H22NO268.1701,found268.1717.2-(2-(1H-indol-1-yl)allyl)cycloheptan-1-one(1c):5.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-10:1)affordascolourlessoil.Yield76%(1.02g).1HNMR(400MHz,CD3C(O)CD3)δ7.62–7.53(m,2H),7.37(d,J=3.3Hz,1H),7.19(ddd,J=8.3,7.0,1.3Hz,1H),7.09(ddd,J=8.0,7.0,1.0Hz,1H),6.59(dd,J=3.4,0.8Hz,1H),5.26(s,1H),5.22(s,1H),3.15(ddd,J=15.2,5.8,1.1Hz,1H),2.58(dd,J=15.4,8.0Hz,1H),2.44(dddd,J=9.7,8.3,5.9,3.4Hz,1H),2.34(dd,J=7.8,4.9Hz,2H),1.91–1.83(m,1H),1.80–1.66(m,3H),1.55–1.22(m,4H).13CNMR(101MHz,CD3C(O)CD3)δ213.4,144.3,136.8,130.2,127.5,122.9,121.6,120.8,112.0,109.3,103.7,49.4,SI-11

1143.4,37.9,30.8,30.0,29.2,24.6.HRMS(ESI)m/z:[M+H]+CalcdforC17H20NO254.1545,found254.1551.2-(2-(1H-indol-1-yl)allyl)cyclooctan-1-one(1d):20.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-10:1)affordascolourlessoil.Yield80%(4.50g).1HNMR(400MHz,CD3C(O)CD3)δ7.57(ddt,J=17.7,8.4,1.0Hz,2H),7.37(d,J=3.3Hz,1H),7.18(ddd,J=8.3,7.0,1.3Hz,1H),7.07(ddd,J=8.0,7.1,1.0Hz,1H),6.58(dd,J=3.3,0.9Hz,1H),5.21(t,J=1.1Hz,1H),5.17(s,1H),3.06(ddd,J=14.8,7.4,1.1Hz,1H),2.70(ddd,J=14.8,6.7,1.0Hz,1H),2.61(dtd,J=10.3,7.0,3.4Hz,1H),2.20–2.14(m,2H),1.971.87(m,1H),1.82–1.72(m,1H),1.66–1.54(m,3H),1.50–1.40(m,3H),1.35–1.26(m,1H),1.16–1.00(m,1H).13CNMR(101MHz,CD3C(O)CD3)δ216.1,143.1,135.8,129.3,126.6,121.9,120.7,119.9,111.1,107.7,102.8,46.8,41.9,37.0,31.9,27.3,24.8,24.6,24.4.HRMS(ESI)m/z:[M+H]+CalcdforC19H24NO282.1858,found282.1879.2-(2-(1H-indol-1-yl)allyl)cyclododecan-1-one(1e):5.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-10:1)affordascolourlessoil.Yield62%(1.05g).1HNMR(400MHz,CD2Cl2)δ7.65(d,J=7.9Hz,1H),7.57(dd,J=8.3,1.0Hz,1H),7.28–7.20(m,2H),7.15(ddd,J=8.0,7.0,1.0Hz,1H),6.63(dd,J=3.3,0.8Hz,1H),5.26(s,1H),5.24(d,J=1.2Hz,1H),3.03(ddd,J=15.2,7.0,1.1Hz,1H),2.72–2.61(m,2H),2.57(qd,J=7.1,4.2Hz,1H),2.16(ddd,J=17.3,7.4,3.5Hz,1H),1.89–1.77(m,1H),1.68(ddd,J=8.0,4.0,2.1Hz,2H),1.39–1.19(m,15H).13CNMR(101MHz,CD2Cl2)δ212.4,143.0,135.9,129.2,126.4,122.1,120.8,120.1,111.2,108.7,103.0,48.5,37.5,35.8,28.6,26.0,25.8,23.9,23.4,23.0,22.2,21.7,21.5.HRMS(ESI)m/z:[M+H]+CalcdforC23H32NO338.2484,found338.2488.2-(2-(5-Methyl-1H-indol-1-yl)allyl)cyclooctan-1-one(1f):3.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-10:1)affordascolourlessoil.Yield82%(726mg).1HNMR(400SI-12

12MHz,CD3C(O)CD3)δ7.43(d,J=8.5Hz,1H),7.37(dt,J=1.7,0.9Hz,1H),7.32(d,J=3.3Hz,1H),7.01(dd,J=8.5,1.7Hz,1H),6.48(dd,J=3.3,0.8Hz,1H),5.18–5.15(m,1H),5.14(s,1H),3.05(ddd,J=14.7,7.3,1.0Hz,1H),2.68(ddd,J=14.7,6.8,1.0Hz,1H),2.61(dtd,J=10.2,7.0,3.3Hz,1H),2.39(s,3H),2.21–2.09(m,2H),1.91(ddt,J=10.7,6.9,3.5Hz,1H),1.76(ddt,J=14.1,9.4,4.9Hz,1H),1.58(dd,J=12.1,8.4Hz,3H),1.45(ddd,J=7.1,5.2,2.6Hz,3H),1.29(ddd,J=14.6,7.9,2.7Hz,1H),1.12–1.03(m,1H).13CNMR(101MHz,CD3C(O)CD3)δ217.2,144.2,135.2,130.6,129.9,127.5,124.5,121.4,111.9,108.0,103.4,47.7,42.9,37.9,32.8,28.3,25.7,25.5,25.4,21.4.HRMS(ESI)m/z:[M+H]+CalcdforC20H26NO296.2014,found296.2023.Methyl1-(3-(2-oxocyclooctyl)prop-1-en-2-yl)-1H-indole-5-carboxylate(1g):1.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-3:1)affordascolourlessoil.Yield59%(200mg).1HNMR(400MHz,CD2Cl2)δ8.39(d,J=1.0Hz,1H),7.91(dd,J=8.7,1.7Hz,1H),7.57(d,J=8.8Hz,1H),7.29(d,J=3.3Hz,1H),6.72(dd,J=3.3,0.9Hz,1H),5.27(s,1H),5.26(s,1H),3.97–3.88(m,3H),3.09(dd,J=14.7,7.3Hz,1H),2.68–2.55(m,2H),2.25–2.11(m,2H),1.91(ddt,J=10.9,7.4,3.4Hz,1H),1.79(ddd,J=9.9,5.8,3.6Hz,1H),1.68–1.60(m,3H),1.55–1.44(m,3H),1.38–1.31(m,1H),1.14–1.04(m,1H).13CNMR(101MHz,CD2Cl2)δ217.4,167.6,142.7,138.2,128.6,128.0,123.6,123.3,122.3,110.8,109.8,104.2,51.7,47.1,42.3,37.2,32.2,27.5,25.0,25.0,24.6.HRMS(ESI)m/z:[M+H]+CalcdforC21H26NO3340.1913,found340.1901.2-(2-(4-methoxy-1H-indol-1-yl)allyl)cyclooctan-1-one(1h):1.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-5:1)affordascolourlessoil.Yield76%(236mg).1HNMR(400MHz,CD2Cl2)δ7.13(d,J=5.9Hz,2H),7.07(d,J=3.0Hz,1H),6.64(d,J=3.3Hz,1H),6.55(d,J=7.0Hz,1H),5.18(d,J=1.1Hz,1H),5.15(s,1H),3.94(s,3H),3.05(dd,J=14.2,6.7Hz,1H),2.67–2.52(m,2H),2.16(t,J=6.6Hz,2H),1.87(ddd,J=14.1,6.9,3.3Hz,1H),1.77(dt,J=16.0,6.0Hz,1H),1.60(dq,J=9.7,4.8Hz,3H),1.45(dq,J=9.3,4.6,3.9Hz,3H),1.31–1.28(m,1H),SI-13

131.06(dd,J=13.4,5.2Hz,1H).13CNMR(101MHz,CD2Cl2)δ217.7,153.4,143.2,137.2,125.0,123.0,119.6,108.8,104.7,100.2,100.0,55.3,47.1,42.4,37.3,32.1,27.6,25.1,25.0,24.7.HRMS(ESI)m/z:[M+H]+CalcdforC20H26NO2312.1964,found312.1958.Methyl1-(3-(2-oxocyclooctyl)prop-1-en-2-yl)-1H-indole-4-carboxylate(1i):1.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-3:1)affordascolourlessoil.Yield76%(236mg).1HNMR(400MHz,CD3C(O)CD3)δ7.86(dd,J=7.5,0.9Hz,1H),7.81(d,J=8.2Hz,1H),7.55(d,J=3.3Hz,1H),7.29(t,J=7.9Hz,1H),7.21(dd,J=3.3,0.8Hz,1H),5.30(s,1H),5.21(s,1H),3.94(s,3H),3.07(ddd,J=15.1,7.8,1.0Hz,1H),2.71(ddd,J=15.1,6.6,1.0Hz,1H),2.65–2.55(m,1H),2.16(dd,J=7.6,4.9Hz,2H),1.96–1.87(m,1H),1.84–1.70(m,1H),1.65–1.54(m,3H),1.50–1.40(m,3H),1.34–1.26(m,1H),1.13–1.02(m,1H).13CNMR(101MHz,CD3C(O)CD3)δ217.1,167.9,143.8,137.6,129.8,124.2,122.6,122.2,116.9,110.2,104.8,51.9,47.8,42.8,38.1,32.9,28.2,25.7,25.6,25.4.HRMS(ESI)m/z:[M+H]+CalcdforC21H26NO3340.1913,found340.1925.2-(2-(4-Methoxy-1H-indol-1-yl)allyl)cyclooctan-1-one(1j):1.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-5:1)affordascolourlessoil.Yield76%(236mg).1HNMR(400MHz,CD3C(O)CD3)δ7.88(dt,J=8.4,0.9Hz,1H),7.69(d,J=3.3Hz,1H),7.56(dd,J=7.4,0.9Hz,1H),7.35(dd,J=8.4,7.4Hz,1H),6.77(dd,J=3.3,0.9Hz,1H),5.35(d,J=1.1Hz,1H),5.26(s,1H),3.07(ddd,J=15.1,7.9,1.0Hz,1H),2.76–2.70(m,1H),2.66–2.57(m,1H),2.24–2.14(m,2H),1.92(ddd,J=10.7,7.1,3.6Hz,1H),1.79(dt,J=13.3,6.5Hz,1H),1.68–1.55(m,3H),1.46(dt,J=5.0,1.9Hz,3H),1.37–1.27(m,1H),1.14–1.01(m,1H).13CNMR(101MHz,CD3C(O)CD3)δ217.0,143.4,136.4,130.9,130.8,126.1,122.8,118.7,117.1,110.9,103.8,101.9,47.9,42.6,37.8,32.7,28.1,25.7,25.6,25.3.HRMS(ESI)m/z:[M+H]+CalcdforC20H23N2O307.1810,found307.1824.SI-14

142-(2-(6-Chloro-1H-indol-1-yl)allyl)cyclooctan-1-one(1k):1.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-10:1)affordascolourlessoil.Yield76%(236mg).1HNMR(400MHz,CD3C(O)CD3)δ7.59(d,J=8.4Hz,1H),7.55(d,J=1.7Hz,1H),7.43(d,J=3.3Hz,1H),7.09(dd,J=8.4,1.8Hz,1H),6.61(d,J=3.4Hz,1H),5.28(s,1H),5.21(s,1H),3.04(dd,J=14.9,7.5Hz,1H),2.69(dd,J=14.9,6.6Hz,1H),2.62(dtd,J=10.3,7.1,3.4Hz,1H),2.19(dd,J=7.6,5.0Hz,2H),1.93(ddt,J=14.2,6.7,4.0Hz,1H),1.81(dq,J=12.9,6.6Hz,1H),1.65–1.55(m,3H),1.46(dd,J=7.0,4.2Hz,3H),1.34(dd,J=12.9,8.7Hz,1H),1.14–1.04(m,1H).13CNMR(101MHz,CD3C(O)CD3)δ217.1,143.8,137.1,128.8,128.7,128.5,122.8,121.4,111.9,109.7,104.0,47.9,42.7,37.9,32.8,28.2,25.8,25.7,25.41.HRMS(ESI)m/z:[M+H]+CalcdforC19H23ClNO316.1468,found316.1460.2-(2-(7-Fluoro-1H-indol-1-yl)allyl)cyclooctan-1-one(1l):1.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-10:1)affordascolourlessoil.Yield76%(236mg).1HNMR(400MHz,CD3C(O)CD3)δ7.58(dd,J=8.7,5.5Hz,1H),7.39(d,J=3.4Hz,1H),7.27(dd,J=10.5,2.4Hz,1H),6.90(ddd,J=9.6,8.6,2.3Hz,1H),6.60(dd,J=3.4,0.9Hz,1H),5.24(t,J=1.1Hz,1H),5.19(s,1H),3.04(ddd,J=14.8,7.5,1.0Hz,1H),2.69(ddd,J=14.8,6.6,1.0Hz,1H),2.62(dtd,J=10.1,6.8,3.3Hz,1H),2.24–2.12(m,2H),1.98–1.88(m,1H),1.85–1.73(m,1H),1.67–1.55(m,3H),1.52–1.42(m,3H),1.38–1.28(m,1H),1.15–1.03(m,1H).13CNMR(101MHz,CD3C(O)CD3)δ217.1,162.0,159.6,143.9,136.8,136.6,128.3,128.2,126.7,122.7,122.6,109.4,109.2,109.2,104.0,98.6,98.3,47.8,42.7,37.8,32.8,28.2,25.7,25.6,25.4.19FNMR(376MHz,CD+3C(O)CD3)δ-121.84.HRMS(ESI)m/z:[M+H]CalcdforC19H22FNO300.1764,found300.1789.2-(2-(5-(4-Methoxyphenyl)-1H-indol-1-yl)allyl)cyclooctan-1-one(1m):1.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-5:1)affordascolourlessoil.Yield70%(271mg).1HNMR(400MHz,CD2Cl2)δ7.82(s,1H),7.62(t,J=SI-15

158.4Hz,3H),7.47(dd,J=8.6,1.6Hz,1H),7.25(d,J=3.3Hz,1H),7.03(d,J=8.7Hz,2H),6.66(d,J=3.2Hz,1H),5.25(s,1H),5.21(s,1H),3.88(s,3H),3.16–3.08(m,1H),2.71–2.60(m,2H),2.27–2.20(m,2H),1.95(ddt,J=10.8,7.2,3.8Hz,1H),1.83(dt,J=15.4,6.0Hz,1H),1.70–1.63(m,3H),1.56–1.46(m,3H),1.37(dq,J=8.8,2.4Hz,1H),1.16–1.08(m,1H).13CNMR(101MHz,CD2Cl2)δ217.7,158.7,143.0,135.1,134.6,133.2,129.8,128.1,127.1,121.6,118.7,114.1,111.6,108.4,103.4,55.3,47.3,42.3,37.2,32.0,27.6,25.3,25.1,24.7.HRMS(ESI)m/z:[M+H]+CalcdforC26H30NO2388.2277,found388.2293.2-(2-(4-Methoxy-1H-indol-1-yl)allyl)cycloheptan-1-one(1n):1.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-5:1)affordascolourlessoil.Yield78%(232mg).1HNMR(400MHz,CD3C(O)CD3)δ7.23(d,J=3.4Hz,1H),7.16–7.10(m,2H),6.62(dd,J=3.3,0.7Hz,1H),6.57(dd,J=7.4,1.1Hz,1H),5.22(t,J=1.1Hz,1H),5.19(s,1H),3.92(s,3H),3.12(ddd,J=15.1,5.7,1.2Hz,1H),2.53(ddd,J=15.1,8.4,0.8Hz,1H),2.46–2.36(m,1H),2.35–2.27(m,2H),1.84(dddd,J=11.9,5.4,3.4,1.4Hz,1H),1.69(tdd,J=12.9,4.4,2.0Hz,3H),1.43(dddt,J=18.9,13.1,7.8,3.0Hz,1H),1.36–1.21(m,3H).13CNMR(101MHz,CD3C(O)CD3)δ213.3,154.3,144.4,138.1,125.9,123.9,120.6,109.5,105.3,101.0,100.9,55.5,49.3,43.4,37.9,30.8,29.9,29.2,24.6.HRMS(ESI)m/z:[M+H]+CalcdforC19H24NO2298.1807,found298.1831.Methyl1-(3-(2-oxocycloheptyl)prop-1-en-2-yl)-1H-indole-5-carboxylate(1o):1.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-3:1)affordascolourlessoil.Yield67%(218mg).1HNMR(400MHz,CD3C(O)CD3)δ8.35(td,J=2.3,1.8,0.9Hz,1H),7.88(dd,J=8.8,1.7Hz,1H),7.62(dt,J=8.8,0.8Hz,1H),7.51(d,J=3.4Hz,1H),6.76(dd,J=3.3,0.8Hz,1H),5.35(t,J=1.0Hz,1H),5.28(s,1H),3.90(s,3H),3.14(ddd,J=15.3,6.1,1.3Hz,1H),2.60(ddd,J=15.3,8.1,0.9Hz,1H),2.44(dddd,J=9.8,8.1,6.1,3.4Hz,1H),2.38–2.29(m,2H),1.92–1.82(m,1H),1.82–1.65(m,3H),1.51–1.39(m,1H),1.38–1.19(m,3H).13CNMR(101MHz,CD3C(O)CD3)δ213.3,168.0,144.0,139.2,129.6,SI-16

16129.4,124.3,124.0,123.1,111.8,110.8,105.0,52.0,49.3,43.5,37.9,31.0,29.9,29.3,24.6.HRMS(ESI)m/z:[M+H]+CalcdforC20H24NO3326.1756,found326.1748.2-(2-(6-Chloro-1H-indol-1-yl)allyl)cycloheptan-1-one(1p):1.0mmolscale,theproductwaspurifiedthroughchromatography(toluene/DCM50:1-10:1)affordascolourlessoil.Yield75%(226mg).1HNMR(400MHz,CD3C(O)CD3)δ7.59(dd,J=8.3,0.5Hz,1H),7.55(d,J=2.0Hz,1H),7.42(d,J=3.4Hz,1H),7.08(dd,J=8.4,1.9Hz,1H),6.61(dd,J=3.3,0.9Hz,1H),5.30(d,J=1.2Hz,1H),5.24(s,1H),3.09(ddd,J=15.2,6.1,1.3Hz,1H),2.57(ddd,J=15.2,8.1,0.9Hz,1H),2.44(dddd,J=9.8,8.1,6.1,3.4Hz,1H),2.35(dd,J=7.8,4.8Hz,2H),1.91–1.82(m,1H),1.79–1.65(m,3H),1.57–1.43(m,1H),1.38–1.24(m,3H).13CNMR(101MHz,CD3C(O)CD3)δ213.3,144.0,137.2,128.8,128.6,128.4,122.8,121.3,111.8,110.3,103.9,49.4,43.4,37.9,31.0,30.0,29.2,24.6.HRMS(ESI)m/z:[M+H]+CalcdforC18H21ClNO302.1312,found301.1329.CycloisomerizationofN-vinylindolesusingCobaloxime/H2systemGeneralprocedureforthecycloisomerizationofN-vinyl-indolesusingCobaloxime/H2systemThecobaltorchromiumcatalystsandN-vinylindole(0.2mmol)wereweighedinaglassvialandtransferredtoaFisher-Portertubeequippedwithamagneticstir-barusing4mLofdryanddegassedbenzene.Thetubewasthenplacedbehindanappropriateblastshieldbeforeitwaspressurizedto2.0atmofH2.Thevesselwasthenimmediatelyventedandrepressurizedandthisoperationwasrepeatedtwentytimes,topushouttheinertatmosphere.Thevesselwaspressurizedto2.0atmofH2for30seconds.Ifnochangeinpressurewasobserved,thetubewaspressurizedto4.8atmofH2,andstirredat60ºCfor3days.(NOTE:ThepressurizedFisher-SI-17

17Portertubeshouldalwaysbeplacedbehindanappropriateblastshield!!!)Aftertheindicatedtime,theFisher-Portertubewascooledtoroomtemperature,H2gaswasventedslowly,thentheapparatuswasdisassembled.Thecrudereactionmixturewasfilteredthroughashortsilicagelplug,andtheplugwaswashedwithethylacetate.Theresultingfiltratewasconcentratedandthecrudereactionmixturewasanalysedby1HNMR(CDCl3,CD2Cl2,C6D6orCD3C(O)CD3)todetermineproductdistributionandselectivity.Unlessstatedotherwise,thecrudeproductwaspurifiedbychromatographyonsilicagel,concentratedunderreducedpressureandstoredneatorasasolutioninacetone.(E)-2-(2-(1H-indol-1-yl)prop-1-en-1-yl)cyclopentan-1-one(3b)Accordingtogeneralprocess,1b(0.2mmol)wassubjectedtothereactioncondition.Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford3basacolorlessoil.Yield65%(31.1mg).1HNMR(400MHz,CD3C(O)CD3)δ7.56(d,J=9.1Hz,2H),7.34(d,J=3.3Hz,1H),7.15(ddd,J=8.1,7.0,1.3Hz,1H),7.05(ddd,J=8.1,7.0,1.0Hz,1H),6.53(dd,J=3.3,0.8Hz,1H),5.49(dd,J=8.8,1.2Hz,1H),3.36–3.26(m,1H),2.48–2.39(m,1H),2.38–2.29(m,1H),2.23(d,J=1.3Hz,3H),2.22–2.15(m,1H),2.15–2.08(m,1H),2.01–1.91(m,1H),1.91–1.79(m,1H).13CNMR(125MHz,CD3C(O)CD3)δ216.6,136.1,136.0,129.3,126.9,121.8,121.7,120.8,119.8,111.41,102.4,48.9,37.0,30.7,20.9,16.9.HRMS(ESI)m/z:[M+H]+CalcdforC16H18NO240.1388,found240.1409.Accordingtogeneralprocess,1a(0.2mmol)wassubjectedtothereactioncondition.Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford:2aasacolorlessoil.Yield40%(20.2mg).3awasisolatedasacolorlessoil.Yield45%(22.8mg).SI-18

181-(2-Methyl-2,3,4,5,6,7-hexahydrobenzofuran-2-yl)-1H-indole(2a)1HNMR(500MHz,CDCl3)δ7.63(d,J=7.7Hz,1H),7.43–7.38(m,2H),7.20–7.16(m,1H),7.15–7.10(m,1H),6.48(d,J=3.4Hz,1H),3.22(d,J=15.2Hz,1H),2.79(d,J=15.4Hz,1H),2.18(dt,J=6.0,3.1Hz,2H),2.11–2.03(m,2H),1.97(s,3H),1.86–1.77(m,2H),1.77–1.68(m,2H).13CNMR(125MHz,CDCl3)δ149.6,134.3,130.3,124.8,121.7,121.2,119.8,112.1,105.5,101.4,96.0,46.0,27.9,23.3,23.1,23.0,22.9.HRMS(ESI)m/z:[M+H]+CalcdforC17H20NO254.1545,found254.1554.(E)-2-(2-(1H-indol-1-yl)prop-1-en-1-yl)cyclohexan-1-one(3a)1HNMR(400MHz,CD3C(O)CD3)δ7.70(dd,J=8.3,0.9Hz,1H),7.56(d,J=7.8Hz,1H),7.34(d,J=3.3Hz,1H),7.20–7.12(m,1H),7.05(ddd,J=7.8,6.9,0.8Hz,1H),6.53(dd,J=3.3,0.9Hz,1H),5.79(dd,J=9.2,1.2Hz,1H),3.64–3.53(m,1H),2.51(tdd,J=12.6,5.8,1.0Hz,1H),2.43–2.36(m,1H),2.27–2.20(m,1H),2.16(d,J=1.2Hz,3H),2.13–2.08(m,1H),1.96–1.87(m,2H),1.79–1.66(m,2H).13CNMR(101MHz,CD3C(O)CD3)δ209.5,136.7,134.8,130.0,127.5,122.9,122.6,121.5,120.6,112.3,103.1,50.5,42.4,35.6,28.4,25.3,17.3.HRMS(ESI)m/z:[M+H]+CalcdforC17H20NO254.1545,found254.1559.Accordingtogeneralprocess,1c(0.2mmol)wassubjectedtothereactioncondition.Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford2casacolorlessoil.Yield46%(24.6mg).3cwasisolatedasacolorlessoil.Yield35%(18.7mg).1-(2-Methyl-3,4,5,6,7,8-hexahydro-2H-cyclohepta[b]furan-2-yl)-1H-indole(2c)1HNMR(400MHz,CD3C(O)CD3)δ7.58–7.54(m,1H),7.50(dq,J=8.3,0.9Hz,1H),7.47(d,J=3.4Hz,1H),7.12(ddd,J=8.3,7.0,1.3Hz,1H),7.04(ddd,J=8.0,7.0,1.1Hz,1H),6.43(dd,J=3.4,0.9Hz,1H),3.24(d,J=15.5Hz,1H),2.99–2.88(m,1H),2.32(t,J=3.8Hz,2H),2.21–2.08(m,2H),1.91(s,3H),1.72-1.68(m,5H),1.33–1.27(m,1H).13CNMR(101MHz,CD3C(O)CD3)δ149.6,134.3,130.3,124.8,121.6,121.2,119.8,112.1,105.5,101.4,96.0,46.0,SI-19

1927.9,23.3,23.1,23.0,22.9.HRMS(ESI)m/z:[M+H]+CalcdforC18H22NO268.1701,found268.1714.(E)-2-(2-(1H-indol-1-yl)prop-1-en-1-yl)cycloheptan-1-one(3c)1HNMR(400MHz,CD3C(O)CD3)δ7.57(td,J=8.0,1.0Hz,2H),7.32(d,J=3.3Hz,1H),7.15(ddd,J=8.4,7.0,1.3Hz,1H),7.05(ddd,J=8.0,7.0,1.1Hz,1H),6.52(dd,J=3.3,0.8Hz,1H),5.82(dd,J=9.4,1.2Hz,1H),3.72(td,J=9.5,4.0Hz,1H),2.65–2.49(m,2H),2.21(d,J=1.2Hz,3H),1.93–1.61(m,7H),1.52–1.42(m,1H).13CNMR(125MHz,CD3C(O)CD3)δ212.4,136.7,134.5,130.0,127.7,124.4,122.6,121.5,120.6,112.1,103.1,51.9,43.4,33.2,29.1,25.1,17.5.HRMS(ESI)m/z:[M+H]+CalcdforC18H22NO268.1701,found268.1722.Accordingtogeneralprocess,1d(0.2mmol)wassubjectedtothereactioncondition.Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford2dasacolorlessoil.Yield53%(29.8mg).3dwasisolatedasacolorlessoil.Yield28%(15.7mg).1-(2-Methyl-3,4,5,6,7,8-hexahydro-2H-cyclohepta[b]furan-2-yl)-1H-indole(2d)1HNMR(400MHz,CD3C(O)CD3)δ7.55(td,J=7.0,1.1Hz,2H),7.49(d,J=3.4Hz,1H),7.12(ddd,J=8.2,7.0,1.4Hz,1H),7.04(ddd,J=7.9,7.1,1.1Hz,1H),6.44(dd,J=3.4,0.8Hz,1H),3.25(d,J=15.7Hz,1H),2.94(d,J=15.6Hz,1H),2.34(tt,J=15.4,7.2Hz,2H),2.23(q,J=5.4,4.3Hz,2H),1.91(s,3H),1.78–1.70(m,2H),1.67–1.56(m,6H).13CNMR(101MHz,CD3C(O)CD3)δ149.6,134.2,130.2,124.6,121.0,120.7,119.3,112.2,105.8,100.8,95.0,46.7,27.2,26.9,26.4,26.0,25.6,25.0,23.7.HRMS(ESI)m/z:[M+H]+CalcdforC19H24NO282.1858,found282.1858.(E)-2-(2-(1H-indol-1-yl)prop-1-en-1-yl)cycloheptan-1-one(3d)1HNMR(400MHz,CD3C(O)CD3)δ7.55(td,J=7.9,1.0Hz,2H),7.32(d,J=3.3Hz,1H),7.15(ddd,J=8.2,7.0,1.3Hz,1H),7.05(ddd,J=8.0,7.0,1.1Hz,1H),6.52(dd,J=3.3,0.8Hz,1H),5.78(dd,J=9.4,1.2Hz,1H),3.72(td,J=9.8,3.7Hz,1H),2.59(ddd,J=13.2,7.7,3.5Hz,1H),2.46(ddd,J=13.2,10.6,3.5Hz,1H),2.23(d,J=1.2Hz,3H),2.13(ddd,J=14.3,7.2,3.7Hz,1H),2.02–1.94(m,1H),1.93–1.45(m,7H),1.32(dddd,J=10.0,6.1,4.4,2.2Hz,1H).SI-20

2013CNMR(101MHz,CD3C(O)CD3)δ215.7,136.6,135.0,130.1,127.7,123.5,122.6,121.6,120.6,112.0,103.2,50.9,41.5,33.1,27.7,27.2,26.4,25.4,17.5.HRMS(ESI)m/z:[M+H]+CalcdforC19H24NO282.1858,found282.1861.Accordingtogeneralprocess,1e(0.2mmol)wassubjectedtothereactioncondition.Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford2easacolorlessoil.Yield52%(35.1mg).32wasisolatedasacolorlessoil.Yield29%(19.5mg).1-(2-Methyl-2,3,4,5,6,7,8,9,10,11,12,13-dodecahydrocyclododeca[b]furan-2-yl)-1H-indole(2e)1HNMR(400MHz,CD2Cl2)δ7.63–7.56(m,1H),7.45(dd,J=8.2,1.1Hz,1H),7.39(d,J=3.4Hz,1H),7.17–7.11(m,1H),7.08(td,J=7.4,7.0,1.1Hz,1H),6.46(dd,J=3.4,0.9Hz,1H),3.20(d,J=15.8Hz,1H),2.76(d,J=15.7Hz,1H),2.35–2.13(m,4H),1.91(s,3H),1.68–1.56(m,2H),1.45–1.27(m,15H).13CNMR(101MHz,CD3C(O)CD3)δ149.9,135.4,131.1,125.7,122.0,121.6,120.4,113.2,108.4,101.9,95.6,45.5,27.9,26.0,25.4,25.4,25.1,25.0,24.8,23.3,22.95,22.74,22.56.HRMS(ESI)m/z:[M+H]+CalcdforC23H32NO338.2484,found338.2485.(E)-2-(2-(1H-indol-1-yl)prop-1-en-1-yl)cyclododecan-1-one(3e)1HNMR(400MHz,CD2Cl2)δ7.59(d,J=7.7Hz,1H),7.47(d,J=8.4Hz,1H),7.17(d,J=3.4Hz,2H),7.08(t,J=7.4Hz,1H),6.54(d,J=3.3Hz,1H),5.72(d,J=9.8Hz,1H),3.64(td,J=9.9,3.6Hz,1H),2.66(td,J=8.2,7.5,3.5Hz,1H),2.58–2.52(m,1H),2.25–2.19(m,3H),1.98(ddd,J=13.4,9.7,6.1Hz,2H),1.83(t,J=12.1Hz,2H),1.70(d,J=9.3Hz,3H),1.36–1.30(m,11H).13CNMR(101MHz,CD2Cl2)δ210.9,134.6,129.0,126.7,122.4,121.9,120.8,119.8,118.2,111.0,102.3,51.1,37.3,30.8,29.7,25.9,25.5,24.1,23.9,23.6,22.3,22.0,17.2.HRMS(ESI)m/z:[M+H]+CalcdforC23H32NO338.2484,found338.2482.SI-21

21CycloisomerizationofN-vinylindoleswithCo(III)/silanesystemTheCo(III)-salencomplexesA-Iwerepreparedaccordingtoknownprocedures.4,5SilanewasusedasastocksolutioninBenzene.GeneralprocedureforCycloisomerizationofN-vinyl-indolesusingCo(III)/silanesystemIntheglovebox,toanoven-dried6mLvialequippedwithastirbarwasaddedtheIndolesubstrates1(0.2mmol)andCo(III)-salenB(12mol%).AstocksolutionofPh2SiH2(2.0mL,12mol%)wasadded.Thevialwassealedwithawhitecapandfurthersealedbyblacktape.Thereactionmixturewasremovedfromglovebox,putinpre-heatedoilbath(60oC)fortheindicatedtime.Thereactionmixturewascooledtoroomtemperature,filteredthroughashortplugofsilicongel,andelutedwithEtOAc.Theresultingfiltratewasconcentratedandthecrudereactionmixturewasanalysedby1HNMR(CDCl3,CD2Cl2orCD3C(O)CD3)todetermineproductdistributionandselectivity.Ratioreportedhereisrefereedtocycloisomerization(2)/isomerization(3).Unlessstatedotherwise,thecrudeproductwaspurifiedbychromatoaphyonsilicagel,concentratedunderreducedpressureandstoredneatorasasolutioninacetone.RepresentativeProcedureforCycloisomerizationreactionon1.0mmolscale.Intheglovebox,toanoven-dried25mLvialequippedwithastirbarwasaddedtheIndolesubstrates1f(1.0mmol)andCo(III)-salenB(12mol%).AstocksolutionofPh2SiH2(10.0mL,12mol%)wasadded.Thevialwassealedwithawhitecapandfurthersealedbyblacktape.Thereactionmixturewasremovedfromglovebox,putinpre-heatedoilbath(60oC)fortheindicatedtime.Thereactionmixturewascooledtoroomtemperature,filteredthroughashortplugofsilicongel,andelutedwithEtOAc.Theresultingfiltratewasconcentratedandthecrudereactionmixturewasanalysedby1HNMR(CD3C(O)CD3)todetermineproductdistributionandselectivity.Purificationbychromatographyonsilicagel(hexane/EtOAc=10:1)afforded2fasacolorlessoil.Yield81%(244.1mg).1HNMR(400MHz,CD3C(O)CD3)δ7.46–7.39(m,SI-22

222H),7.34(dt,J=1.7,0.9Hz,1H),6.95(dd,J=8.5,1.7Hz,1H),6.33(dd,J=3.4,0.9Hz,1H),3.23(d,J=15.6Hz,1H),2.91(d,J=15.6Hz,1H),2.38(s,3H),2.37–2.31(m,2H),2.26–2.19(m,2H),1.89(s,3H),1.77–1.70(m,2H),1.68–1.56(m,6H).13CNMR(125MHz,CD3C(O)CD3)δ150.6,133.6,131.5,129.1,125.6,123.6,121.3,112.8,106.7,101.3,95.9,47.6,28.2,27.9,27.4,27.0,26.5,26.0,24.6,21.4.HRMS(ESI)m/z:[M+H]+CalcdforC20H26NO296.2014,found296.2019.(E)-2-(2-(1H-indol-1-yl)prop-1-en-1-yl)cyclopentan-1-one(3b)Accordingtogeneralprocedure,1b(0.2mmol)wassubjectedtothereactioncondition.Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford3basacolorlessoil.Yield66%(32.0mg).1HNMR(400MHz,CD3C(O)CD3)δ7.56(d,J=9.1Hz,2H),7.34(d,J=3.3Hz,1H),7.15(ddd,J=8.1,7.0,1.3Hz,1H),7.05(ddd,J=8.1,7.0,1.0Hz,1H),6.53(dd,J=3.3,0.8Hz,1H),5.49(dd,J=8.8,1.2Hz,1H),3.36–3.26(m,1H),2.48–2.39(m,1H),2.38–2.29(m,1H),2.23(d,J=1.3Hz,3H),2.22–2.15(m,1H),2.15–2.08(m,1H),2.01–1.91(m,1H),1.91–1.79(m,1H).13CNMR(125MHz,CD3C(O)CD3)δ216.6,136.1,136.0,129.3,126.9,121.8,121.7,120.8,119.8,111.41,102.4,48.9,37.0,30.7,20.9,16.9.Accordingtogeneralprocess,1a(0.2mmol)wassubjectedtothereactioncondition.Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford2aasacolorlessoil.Yield50%(25.3mg).3awasisolatedasacolorlessoil.Yield30%(15.2mg).1-(2-Methyl-2,3,4,5,6,7-hexahydrobenzofuran-2-yl)-1H-indole(2a)SI-23

231HNMR(500MHz,CDCl3)δ7.63(d,J=7.7Hz,1H),7.43–7.38(m,2H),7.20–7.16(m,1H),7.15–7.10(m,1H),6.48(d,J=3.4Hz,1H),3.22(d,J=15.2Hz,1H),2.79(d,J=15.4Hz,1H),2.18(dt,J=6.0,3.1Hz,2H),2.11–2.03(m,2H),1.97(s,3H),1.86–1.77(m,2H),1.77–1.68(m,2H).13CNMR(125MHz,CDCl3)δ149.6,134.3,130.3,124.8,121.7,121.2,119.8,112.1,105.5,101.4,96.0,46.0,27.9,23.3,23.1,23.0,22.9.(E)-2-(2-(1H-indol-1-yl)prop-1-en-1-yl)cyclopentan-1-one(3a)1HNMR(400MHz,CD3C(O)CD3)δ7.70(dd,J=8.3,0.9Hz,1H),7.56(d,J=7.8Hz,1H),7.34(d,J=3.3Hz,1H),7.20–7.12(m,1H),7.05(ddd,J=7.8,6.9,0.8Hz,1H),6.53(dd,J=3.3,0.9Hz,1H),5.79(dd,J=9.2,1.2Hz,1H),3.64–3.53(m,1H),2.51(tdd,J=12.6,5.8,1.0Hz,1H),2.43–2.36(m,1H),2.27–2.20(m,1H),2.16(d,J=1.2Hz,3H),2.13–2.08(m,1H),1.96–1.87(m,2H),1.79–1.66(m,2H).13CNMR(101MHz,CD3C(O)CD3)δ209.5,136.7,134.8,130.0,127.5,122.9,122.6,121.5,120.6,112.3,103.1,50.5,42.4,35.6,28.4,25.3,17.3.Accordingtogeneralprocess,1c(0.2mmol)wassubjectedtothereactioncondition.Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford2casacolorlessoil.Yield83%(44.3mg).3cwasisolatedasacolorlessoil.Yield11%(5.8mg).1-(2-Methyl-3,4,5,6,7,8-hexahydro-2H-cyclohepta[b]furan-2-yl)-1H-indole(2c)1HNMR(400MHz,CD3C(O)CD3)δ7.58–7.54(m,1H),7.50(dq,J=8.3,0.9Hz,1H),7.47(d,J=3.4Hz,1H),7.12(ddd,J=8.3,7.0,1.3Hz,1H),7.04(ddd,J=8.0,7.0,1.1Hz,1H),6.43(dd,J=3.4,0.9Hz,1H),3.24(d,J=15.5Hz,1H),2.99–2.88(m,1H),2.32(t,J=3.8Hz,2H),2.21–2.08(m,2H),1.91(s,3H),1.72-1.68(m,5H),1.33–1.27(m,1H).13CNMR(101MHz,CD3C(O)CD3)δ149.6,134.3,130.3,124.8,121.6,121.2,119.8,112.1,105.5,101.4,96.0,46.0,27.9,23.3,23.1,23.0,22.9.(E)-2-(2-(1H-indol-1-yl)prop-1-en-1-yl)cycloheptan-1-one(3c)1HNMR(400MHz,CD3C(O)CD3)δ7.57(td,J=8.0,1.0Hz,2H),7.32(d,J=3.3Hz,1H),7.15(ddd,J=8.4,7.0,1.3Hz,1H),7.05(ddd,J=8.0,7.0,1.1Hz,1H),6.52(dd,J=3.3,0.8Hz,1H),5.82(dd,J=9.4,1.2Hz,1H),3.72(td,J=9.5,4.0Hz,1H),2.65–2.49(m,2H),2.21(d,JSI-24

24=1.2Hz,3H),1.93–1.61(m,7H),1.52–1.42(m,1H).13CNMR(125MHz,CD3C(O)CD3)δ212.4,136.7,134.5,130.0,127.7,124.4,122.6,121.5,120.6,112.1,103.1,51.9,43.4,33.2,29.1,25.1,17.5.Accordingtogeneralprocess,1d(0.2mmol)wassubjectedtothereactioncondition.Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford2dasacolorlessoil.Yield85%(47.8mg).3dwasisolatedasacolorlessoil.Yield10%(5.6mg).1-(2-Methyl-3,4,5,6,7,8-hexahydro-2H-cyclohepta[b]furan-2-yl)-1H-indole(2d)1HNMR(400MHz,CD3C(O)CD3)δ7.55(td,J=7.0,1.1Hz,2H),7.49(d,J=3.4Hz,1H),7.12(ddd,J=8.2,7.0,1.4Hz,1H),7.04(ddd,J=7.9,7.1,1.1Hz,1H),6.44(dd,J=3.4,0.8Hz,1H),3.25(d,J=15.7Hz,1H),2.94(d,J=15.6Hz,1H),2.34(tt,J=15.4,7.2Hz,2H),2.23(q,J=5.4,4.3Hz,2H),1.91(s,3H),1.78–1.70(m,2H),1.67–1.56(m,6H).13CNMR(101MHz,CD3C(O)CD3)δ149.6,134.2,130.2,124.6,121.0,120.7,119.3,112.2,105.8,100.8,95.0,46.7,27.2,26.9,26.4,26.0,25.6,25.0,23.7.(E)-2-(2-(1H-indol-1-yl)prop-1-en-1-yl)cycloheptan-1-one(3d)1HNMR(400MHz,CD3C(O)CD3)δ7.55(td,J=7.9,1.0Hz,2H),7.32(d,J=3.3Hz,1H),7.15(ddd,J=8.2,7.0,1.3Hz,1H),7.05(ddd,J=8.0,7.0,1.1Hz,1H),6.52(dd,J=3.3,0.8Hz,1H),5.78(dd,J=9.4,1.2Hz,1H),3.72(td,J=9.8,3.7Hz,1H),2.59(ddd,J=13.2,7.7,3.5Hz,1H),2.46(ddd,J=13.2,10.6,3.5Hz,1H),2.23(d,J=1.2Hz,3H),2.13(ddd,J=14.3,7.2,3.7Hz,1H),2.02–1.94(m,1H),1.93–1.45(m,7H),1.32(dddd,J=10.0,6.1,4.4,2.2Hz,1H).13CNMR(101MHz,CD3C(O)CD3)δ215.7,136.6,135.0,130.1,127.7,123.5,122.6,121.6,120.6,112.0,103.2,50.9,41.5,33.1,27.7,27.2,26.4,25.4,17.5.SI-25

25Accordingtogeneralprocess,1e(0.2mmol)wassubjectedtothereactioncondition.Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford2easacolorlessoil.Yield72%(48.5mg).3ewasisolatedasacolorlessoil.Yield22%(14.8mg).1-(2-Methyl-2,3,4,5,6,7,8,9,10,11,12,13-dodecahydrocyclododeca[b]furan-2-yl)-1H-indole(2e)1HNMR(400MHz,CD2Cl2)δ7.63–7.56(m,1H),7.45(dd,J=8.2,1.1Hz,1H),7.39(d,J=3.4Hz,1H),7.17–7.11(m,1H),7.08(td,J=7.4,7.0,1.1Hz,1H),6.46(dd,J=3.4,0.9Hz,1H),3.20(d,J=15.8Hz,1H),2.76(d,J=15.7Hz,1H),2.35–2.13(m,4H),1.91(s,3H),1.68–1.56(m,2H),1.45–1.27(m,15H).13CNMR(101MHz,CD3C(O)CD3)δ149.9,135.4,131.1,125.7,122.0,121.6,120.4,113.2,108.4,101.9,95.6,45.5,27.9,26.0,25.4,25.4,25.1,25.0,24.8,23.3,23.0,22.7,22.6.(E)-2-(2-(1H-indol-1-yl)prop-1-en-1-yl)cyclododecan-1-one(3e)1HNMR(400MHz,CD2Cl2)δ7.59(d,J=7.7Hz,1H),7.47(d,J=8.4Hz,1H),7.17(d,J=3.4Hz,2H),7.08(t,J=7.4Hz,1H),6.54(d,J=3.3Hz,1H),5.72(d,J=9.8Hz,1H),3.64(td,J=9.9,3.6Hz,1H),2.66(td,J=8.2,7.5,3.5Hz,1H),2.58–2.52(m,1H),2.25–2.19(m,3H),1.98(ddd,J=13.4,9.7,6.1Hz,2H),1.83(t,J=12.1Hz,2H),1.70(d,J=9.3Hz,3H),1.36–1.30(m,11H).13CNMR(101MHz,CD2Cl2)δ210.9,134.6,129.0,126.7,122.4,121.9,120.8,119.8,118.2,111.0,102.3,51.1,37.3,30.8,29.7,25.9,25.5,24.1,23.9,23.6,22.3,22.0,17.22g-2pwerepreparedaccordingtothegeneralprocedure,theratioofcyclo-isomerizationtoisomerizationwasdeterminedbythecrude1H-NMR,theyieldreferstotheisolatedyieldofthemajorproduct.Methyl1-(2-methyl-2,3,4,5,6,7,8,9-octahydrocycloocta[b]furan-2-yl)-1H-indole-5-carboxylate(2g)SI-26

26Accordingtogeneralprocedure,1g(0.1mmol)wassubjectedtothereactioncondition.Ratio7.2:1,Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1to3:1)afford2gasacolorlessoil.Yield56%(19.0mg).1HNMR(400MHz,CD3C(O)CD3)δ8.31(d,J=1.7Hz,1H),7.81(dd,J=8.8,1.7Hz,1H),7.66–7.60(m,2H),6.61(dd,J=3.4,0.8Hz,1H),3.87(s,3H),3.24(d,J=15.8Hz,1H),3.01(d,J=16.0Hz,1H),2.37(q,J=6.2Hz,2H),2.26–2.20(m,2H),1.94(s,3H),1.74(t,J=5.9Hz,2H),1.65–1.56(m,6H).13CNMR(101MHz,CD3C(O)CD3)δ168.1,150.6,137.6,130.7,127.4,124.3,123.1,122.6,112.9,107.1,103.3,96.3,51.9,47.9,28.1,27.9,27.4,26.9,26.5,25.9,24.6.HRMS(ESI)m/z:[M+H]+CalcdforC21H26NO3340.1913,found340.1908.4-Methoxy-1-(2-methyl-2,3,4,5,6,7,8,9-octahydrocycloocta[b]furan-2-yl)-1H-indole(2h)Accordingtogeneralprocedure,1h(0.1mmol)wassubjectedtothereactioncondition.Ratio7.5:1,Theproductwaspurifiedthroughchromatography(hexane/EtOAc=6:1)afford2hasacolorlessoil.Yield75%(23.3mg).1HNMR(400MHz,CD3C(O)CD3)δ7.38(d,J=3.4Hz,1H),7.14(dd,J=8.4,0.7Hz,1H),7.04(t,J=8.0Hz,1H),6.55(d,J=7.7Hz,1H),6.48(d,J=3.4Hz,1H),3.90(s,3H),3.23(d,J=15.6Hz,1H),2.93(d,J=15.6Hz,1H),2.40–2.27(m,2H),2.22(td,J=6.5,4.1Hz,2H),1.90(s,3H),1.77–1.70(m,2H),1.65–1.53(m,6H).13CNMR(101MHz,CD3C(O)CD3)δ153.46,149.65,135.54,122.97,122.04,120.69,105.90,105.63,99.38,98.06,95.10,54.50,46.80,27.26,26.99,26.52,26.04,25.62,25.03,23.73.HRMS(ESI)m/z:[M+H]+CalcdforC20H26NO2312.1964,found312.1962.Methyl1-(2-methyl-2,3,4,5,6,7,8,9-octahydrocycloocta[b]furan-2-yl)-1H-indole-4-carboxylate(2i)Accordingtogeneralprocedure,1i(0.1mmol)wassubjectedtothereactioncondition.Ratio6.7:1,Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1to3:1)afford2iasacolorlessoil.Yield61%(20.7mg).1HNMR(400MHz,CD3C(O)CD3)δ7.84(d,J=7.8Hz,2H),7.68(d,J=3.4Hz,1H),SI-27

277.23(t,J=7.9Hz,1H),7.09(d,J=3.3Hz,1H),3.92(s,3H),3.24(d,J=15.8Hz,1H),3.00(d,J=15.8Hz,1H),2.37(dt,J=14.4,7.7Hz,2H),2.24(q,J=5.6,4.7Hz,2H),1.95(s,3H),1.73(q,J=6.0Hz,2H),1.66–1.56(m,6H).13CNMR(101MHz,CD3C(O)CD3)δ168.0,150.6,136.0,130.6,127.9,123.6,122.5,121.2,118.0,107.0,103.0,96.2,51.8,47.9,28.1,28.0,27.4,26.9,26.5,25.9,24.6.HRMS(ESI)m/z:[M+H]+CalcdforC21H26NO3340.1913,found340.1915.1-(2-Methyl-2,3,4,5,6,7,8,9-octahydrocycloocta[b]furan-2-yl)-1H-indole-4-carbonitrile(2j)Accordingtogeneralprocedure,1j(0.1mmol)wassubjectedtothereactioncondition.Ratio6.1:1,Theproductwaspurifiedthroughchromatography(hexane/EtOAc=7:1)afford2jasacolorlessoil.Yield52%(15.9mg).1HNMR(400MHz,CD3C(O)CD3)δ7.92(d,J=8.4Hz,1H),7.79(d,J=3.4Hz,1H),7.52(dd,J=7.4,0.8Hz,1H),7.29(dd,J=8.5,7.4Hz,1H),6.64(dd,J=3.4,0.9Hz,1H),3.24(d,J=15.9Hz,1H),3.04(d,J=16.0Hz,1H),2.42–2.31(m,2H),2.23(q,J=6.5,5.9Hz,2H),1.96(s,3H),1.73(p,J=5.9Hz,2H),1.67–1.53(m,6H).13CNMR(101MHz,CD3C(O)CD3)δ150.6,134.9,132.0,129.0,125.6,122.0,118.9,118.3,107.3,103.9,100.2,96.5,48.0,28.1,28.0,27.4,26.9,26.5,25.9,24.6.HRMS(ESI)m/z:[M+H]+CalcdforC20H23N2O307.1810,found307.1816.6-Chloro-1-(2-methyl-2,3,4,5,6,7,8,9-octahydrocycloocta[b]furan-2-yl)-1H-indole(2k)Accordingtogeneralprocedure,1k(0.1mmol)wassubjectedtothereactioncondition.Ratio>20:1,Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford2kasacolorlessoil.Yield65%(15.8mg).Whenthereactionwasrunat80oC,ratio11:1.Yield80%determinedby1H-NMR.1HNMR(400MHz,CD3C(O)CD3)δ7.60(dd,J=1.8,0.9Hz,1H),7.56(d,J=8.4Hz,1H),7.53(d,J=3.4Hz,1H),7.06(dd,J=8.4,1.9Hz,1H),6.47(dd,J=3.4,0.9Hz,1H),3.21(d,J=15.8Hz,1H),2.95(d,J=15.8Hz,1H),2.36(tt,J=6.1,1.6Hz,2H),2.29–2.22(m,2H),1.93(s,3H),1.75(d,J=6.9Hz,2H),1.68–1.58(m,6H).13CNMR(101MHz,CD3C(O)CD3)δ150.6,135.6,129.8,127.6,126.8,122.8,120.8,SI-28

28113.1,107.0,102.2,96.1,47.8,28.0,27.8,27.29,27.0,26.6,26.0,24.7.HRMS(ESI)m/z:[M+H]+CalcdforC19H23ClNO316.1468,found316.1467.6-Fluoro-1-(2-methyl-2,3,4,5,6,7,8,9-octahydrocycloocta[b]furan-2-yl)-1H-indole(2l)Accordingtogeneralprocedure,1l(0.1mmol)wassubjectedtothereactioncondition.Ratio10:1,Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford2lasacolorlessoil.Yield71%(15.9mg).1HNMR(400MHz,CD3C(O)CD3)δ7.55(dd,J=8.6,5.6Hz,1H),7.49(d,J=3.5Hz,1H),7.28(dd,J=10.7,1.7Hz,1H),6.94–6.81(m,1H),6.46(d,J=3.5Hz,1H),3.21(d,J=15.8Hz,1H),2.94(d,J=15.8Hz,1H),2.37(ddd,J=20.8,14.5,6.4Hz,2H),2.29–2.19(m,2H),1.91(s,3H),1.73(q,J=6.5,6.0Hz,2H),1.70–1.55(m,6H).13CNMR(125MHz,CD3C(O)CD3)δ159.1(d,JF=245.0Hz),149.7,134.2(d,JF=12.5Hz),126.8,125.4(d,JF=3.8Hz),121.6(d,JF=11.2Hz),107.8(d,JF=25.0Hz),106.0,101.2,98.6(d,JF=27.5Hz),95.2,46.5,27.2,26.9,26.5,26.0,25.6,25.0,23.7.19FNMR(376MHz,CD3C(O)CD3)δ-122.70.HRMS(ESI-)m/z:[M+H]+CalcdforC19H22FNO300.1764,found300.1778.5-(4-Methoxyphenyl)-1-(2-methyl-2,3,4,5,6,7,8,9-octahydrocycloocta[b]furan-2-yl)-1H-indole(2m)Accordingtogeneralprocedure,1l(0.1mmol)wassubjectedtothereactioncondition.Ratio6.8:1,Theproductwaspurifiedthroughchromatography(hexane/EtOAc=4:1)afford2masacolorlessoil.Yield68%(26.3mg).1HNMR(400MHz,CD3C(O)CD3)δ7.77(d,J=1.8Hz,1H),7.64–7.57(m,3H),7.51(d,J=3.4Hz,1H),7.38(dd,J=8.6,1.8Hz,1H),7.00(d,J=8.8Hz,2H),6.48(d,J=4.0Hz,1H),3.84(s,3H),3.28(d,J=15.7Hz,1H),3.04–2.91(m,1H),2.37(ddd,J=8.3,7.0,5.3Hz,2H),2.25(q,J=5.4,4.5Hz,2H),1.94(s,3H),1.79–1.72(m,2H),1.67–1.55(m,6H).13CNMR(125MHz,CD3C(O)CD3)δ159.6,150.6,135.6,134.4,133.4,131.8,128.8,126.3,121.4,119.4,115.0,113.4,106.8,102.2,96.0,55.6,47.7,28.2,27.9,27.4,27.0,26.6,26.0,24.6.HRMS(ESI)m/z:[M+H]+CalcdforC26H30NO2388.2277,found388.2280.SI-29

294-Methoxy-1-(2-methyl-3,4,5,6,7,8-hexahydro-2H-cyclohepta[b]furan-2-yl)-1H-indole(2n)Accordingtogeneralprocedure,1n(0.1mmol)wassubjectedtothereactioncondition.Ratio6.5:1,Theproductwaspurifiedthroughchromatography(hexane/EtOAc=7:1)afford2nasacolorlessoil.Yield69%(20.5mg).1HNMR(400MHz,CD3C(O)CD3)δ7.37(d,J=3.4Hz,1H),7.14–7.02(m,2H),6.57(dd,J=7.5,0.9Hz,1H),6.49(dd,J=3.4,0.8Hz,1H),3.92(s,3H),3.23(d,J=15.4Hz,1H),2.94(d,J=15.7Hz,1H),2.33(s,2H),2.13(d,J=5.3Hz,2H),1.90(s,3H),1.80–1.64(m,6H).13CNMR(101MHz,CD3C(O)CD3)δ153.5,150.6,135.6,134.1,130.7,127.9,123.0,122.2,108.0,105.6,99.4,98.1,94.9,54.5,48.6,27.7,26.9,26.0,25.8.HRMS(ESI)m/z:[M+H]+CalcdforC19H24NO2298.1807,found298.1805.Methyl1-(2-methyl-3,4,5,6,7,8-hexahydro-2H-cyclohepta[b]furan-2-yl)-1H-indole-5-carboxylate(2o)Accordingtogeneralprocedure,1o(0.1mmol)wassubjectedtothereactioncondition.Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford2oasacolorlessoil.Yield58%(18.9mg).1HNMR(400MHz,CD3C(O)CD3)δ8.32(dd,J=1.7,0.7Hz,1H),7.84(dd,J=8.8,1.7Hz,1H),7.67–7.57(m,2H),6.62(dd,J=3.5,0.8Hz,1H),3.89(s,3H),3.24(d,J=15.9Hz,1H),3.02(d,J=17.9Hz,1H),2.41–2.31(m,2H),2.19–2.10(m,2H),1.95(s,3H),1.72(q,J=2.6Hz,6H).13CNMR(101MHz,CD3C(O)CD3)δ168.1,151.6,137.6,130.7,127.4,124.2,123.2,122.6,112.9,109.1,103.2,96.1,51.9,49.7,28.6,27.8,26.9,26.6.HRMS(ESI)m/z:[M+H]+CalcdforC20H24NO3326.1756,found326.1764.6-Chloro-1-(2-methyl-3,4,5,6,7,8-hexahydro-2H-cyclohepta[b]furan-2-yl)-1H-indole(2p)Accordingtogeneralprocedure,1p(0.1mmol)wassubjectedtothereactioncondition.Ratio13:1,Theproductwaspurifiedthroughchromatography(hexane/EtOAc=10:1)afford2pasacolorlessoil.Yield68%(20.5mg).1HNMR(400MHz,CD3C(O)CD3)δ7.62–7.54(m,2H),7.52(d,J=3.4Hz,1H),7.08(dd,J=8.5,1.8Hz,1H),6.48(dd,J=3.4,SI-30

300.9Hz,1H),3.19(d,J=15.9Hz,1H),2.98(d,J=16.0Hz,1H),2.39–2.27(m,2H),2.16(t,J=7.1Hz,2H),1.94(s,3H),1.82–1.65(m,6H).13CNMR(101MHz,CD3C(O)CD3)δ150.8,128.8,127.9,126.8,125.9,121.8,119.8,112.2,108.1,101.2,95.0,48.6,27.7,26.9,26.0,25.7.HRMS(ESI)m/z:[M+H]+CalcdforC18H21ClNO301.1312,found301.1314.SI-31

31MechanisticStudiesA.Incorporationofdeuterium.DeuteriumincorporationexperimentswererunaccordingtothegeneralprocedureunderH2exceptunderD12.TheDincorporationwasdeterminedfromcrudeH-NMRofthereactionmixture(measuringtheamountof1Hsignalwasmissing)andfurtherverifiedby2H-NMR.B.Reactiontimeandtheratioofproduct:Insideglovebox,indolesubstrates1(0.1mmol)andCo(III)-salenB(12mol%)wereweightout,followedbyadditionofPh2SiH2instocksolutioninC6D6(1.0mL,12mol%),thenthereactionmixturewastransferintoaJ-Youngtube,andtheJ-Youngtubewasplacedunderpre-heatedoilbath(60oC),crude1H-NMRwastakenforindicatedtime,theresultsareshowingbelow.C.Interconversionofproducts:Thosefourcontrolledreactionswererunaccordingtothegeneralprocedureundersalen-Co(III)/silaneconditions.Theyieldoftheproductwasdeterminedby1HNMRofthecrudereactionmixturewithinternalstandard.SI-32

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33References1.Yao,C.;Dahmen,T.;Gansäuer,A.;Norton,J.Anti-Markovnikovalcoholsviaepoxidehydrogenationthroughcooperativecatalysis.Science2019,364,764-767.2.Li,G.;Estes,D.P.;Norton,J.R.;Ruccolo,S.;Sattler,A.;Sattler,W.DihydrogenActivationbyCobaloximeswithVariousAxialLigands.Inorg.Chem.2014,53,10743-10747.3.Floriani,C.;Puppis,M.;Calderazzo,F.N,N′-Ethylenebis(salicylideneiminato)cobalt(II).Reduction,oxidationandconversionintoalkylandacylderivatives.J.Organomet.Chem.1968,12,209-223.4.Schaus,S.E.;Brandes,B.D.;Larrow,J.F.;Tokunaga,M.;Hansen,K.B.;Gould,A.E.;Furrow,M.E.;Jacobsen,E.N.Highlyselectivehydrolytickineticresolutionofterminalepoxidescatalyzedbychiral(salen)CoIIIcomplexes.Practicalsynthesisofenantioenrichedterminalepoxidesand1,2-diols.J.Am.Chem.Soc.2002,124,1307-1315.5.Tanyeli,C.;Akhmedov,İ.M.;Yazıcıoğlu,E.Y.One-potsynthesisofN-substituted2-methyl-4,5,6,7-tetrahydroindolederivatives.TetrahedronLett.2004,45,9627-9629.6.Pan,Y.;Lu,H.;Fang,Y.;Fang,X.;Chen,L.;Qian,J.;Wang,J.;Li,C.Synthesisofpyrrolesviacopper-catalyzedcouplingofamineswithbromoenones.Synthesis2007,2007,1242-1246.7.Li,H.;Boonnak,N.;Padwa,A.N-AlkenylIndolesasUsefulIntermediatesforAlkaloidSynthesis.J.Org.Chem.2011,76,9488-9496.SI-34

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