C – O Bond Formation from Azulenecarboxylic Acids and - C et al. - Unknown - Unknown

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SupportingInformationIridium(III)-CatalyzedSequentialC(2)-ArylationandIntramolecularC–OBondFormationfromAzulenecarboxylicAcidsandDiaryliodoniumSaltsAccesstoAzulenofuranonesChanyoungMaeng,‡HyungJinSeo,‡HanealJeong,‡KyungsupLee,‡HeeChanNoh,‡andPhilHoLee†,‡,*†TheKoreanAcademyofScienceandTechnology,Seongnam13630,RepublicofKorea‡DepartmentofChemistry,KangwonNationalUniversity,Chuncheon24341,RepublicofKorea*Correspondingauthors.E-mail:phlee@kangwon.ac.kr.S1

1Contents1.ExperimentalSection····················································································S32.GeneralProcedure·························································································S43.StudiesontheKineticIsotopeEffect··································································S154.X-rayCrystallography················································································S165.References································································································S196.1H,13C,and19FNMRdata············································································S20S2

21.ExperimentalSectionGeneral:Commercialavailablereagentswereusedwithoutpurification.Azulenecarboxylicacids(1)1anddiaryliodoniumsalts(2)2werepreparedbyreportedmethod.Allreactionmixtureswerestirredmagneticallyandweremonitoredbythin-layerchromatographyusingsilicagelpre-coatedglassplates,whichwerevisualizedwithUVlightandthen,developedusingeitheriodineorasolutionofanisaldehyde.Forreactionsthatrequireheating,oilbathwasusedasthesourceofheating.Flashcolumnchromatographywascarriedoutusingsilicagel(230-400mesh).1HNMR(400MHz),13C{1H}NMR(100MHz),and19FNMR(377MHz)spectrawererecordedonNMRspectrometer.Deuteratedchloroform,dimethylsulfoxide,andacetonewereusedasthesolvents,andchemicalshiftvalues(δ)arereportedinpartspermillionrelativetotheresidualsignalsofthesesolvent[δ7.26for1H(chloroform-d),δ2.50for1H(DMSO-d11316),δ2.05forH(acetoned-d6),δ77.2forC{H}(chloroform-d),δ39.5for13C{1H}(DMSO-d1316),andδ29.8,206.3forC{H}(acetone-d6)].InfraredspectrawererecordedonFT-IRspectrometeraseitherathinfilmpressedbetweentwosodiumchlorideplatesorasasolidsuspendedinapotassiumbromidedisk.Highresolutionmassspectra(HRMS)wereobtainedbyelectronimpact(EI)ionizationtechnique(magneticsector-electricsectordoublefocusingmassanalyzer)fromtheKBSI(KoreaBasicScienceInstituteDaeguCenter).Meltingpointsweredeterminedinopencapillarytube.S3

32.GeneralProcedureProcedurefortheIr-CatalyzedArylationReactionofAzulene-1-carboxylicAcidswithDiaryliodoniumSaltsOOOH[Cp*IrCl2]2(4.0mol%)OHAgOAc(1.0equiv)3+IXNaHPORH324(1.0equiv)RR12DMF,60oR1C,2hR2X=OTf,BF4R2123Adriedtesttubeequippedwithamagneticstirrerwaschargedwithazulene-1-carboxylicacids(1)(0.2mmol),diaryliodoniumsalts(2)(0.24mmol),[Cp*IrCl2]2(4.0mol%,6.4mg),AgOAc(1.0equiv,33.4mg),Na2HPO4(1.0equiv,28.4mg),andDMF(1.0mL)underanitrogenatmosphere.Afterbeingstirredat60°Cfor2h,thereactionmixturewascooledtoroomtemperature,filteredthroughapadofCelite,andconcentratedunderreducedpressure.Thecrudeproductwaspurifiedbycolumnchromatographyonsilicagel.Procedureforscale-upreactionAdriedtesttubeequippedwithamagneticstirrerwaschargedwithazulene-1-carboxylicacid(1a)(1.0mmol,172.2mg),diphenyliodoniumtriflate(2a)(1.2mmol,516.2mg),[Cp*IrCl2]2(4.0mol%,31.9mg),AgOAc(1.0equiv,166.9mg),Na2HPO4(1.0equiv,142mg),andDMF(5.0mL)underanitrogenatmosphere.Afterbeingstirredat60°Cfor2h,thereactionmixturewascooledtoroomtemperature,filteredthroughapadofCelite,andconcentratedunderreducedpressure.Thefiltratewasconcentratedunderreducedpressure,andtheresiduewaspurifiedbysilicagelfreshcolumnchromatography(Acetone:Hexane=1:4)togive3a(216mg,87%).O2-Phenylazulene-1-carboxylicacid(3a):Yield:43.2mg(87%);Rf=0.2OH(Acetone:Hexane=1:4);Bluesolid;Meltingpoint:228-230oC;1HNMR(400PhMHz,CDCl3)δ9.61(d,J=10.0Hz,1H),8.43(d,J=9.6Hz,1H),7.79(t,J=9.8Hz,1H),7.67-7.45(m,2H),7.59(t,J=10.0Hz,1H),7.51-7.38(m,4H),7.34(s,1H);13C{1H}NMR(100MHz,CDCl3)δ170.0,154.9,143.6,143.3,138.7,138.2,137.9,137.8,130.0,128.7,128.1,127.9,127.8,120.5,113.1;IR(film):2916,2360,1646,1455,1416,1341,1240,768,697cm-1;HRMS(EI)m/z:[M]+CalcdforC17H12O2248.0837;Found248.0836.S4

4O2-(o-Tolyl)azulene-1-carboxylicacid(3b):Yield:41.0mg(78%);Rf=0.2OH(Acetone:Hexane=1:4);Bluesolid;Meltingpoint:220-222oC;1HNMR(400MHz,CDCl3)δ9.70(d,J=10.0Hz,1H),8.44(d,J=9.6Hz,1H),7.82(t,JMe=9.8Hz,1H),7.62(t,J=10.0Hz,1H),7.51(t,J=9.6Hz,1H),7.32-7.27(m,4H),7.21(s,1H),2.20(s,3H);13C{1H}NMR(100MHz,DMSO-d6)δ166.4,153.6,142.1,140.7,139.1,138.8,138.0,137.2,135.2,129.3,129.0,127.8,127.4,127.1,125.0,119.6,115.8,20.0;IR(film):1646,1454,1433,1413,1341,1239,768,605cm-1;HRMS(EI)m/z:[M]+CalcdforC18H14O2262.0994;Found262.0997.O2-(m-Tolyl)azulene-1-carboxylicacid(3c):Yield:40.4mg(77%);Rf=0.2OHMe(Acetone:Hexane=1:4);Bluesolid;Meltingpoint:226-228oC;1HNMR(400MHz,DMSO-d6)δ9.27(d,J=9.9Hz,1H),8.55(d,J=9.4Hz,1H),7.87(t,J=9.8Hz,1H),7.60(t,J=9.9Hz,1H),7.53(t,J=9.7Hz,1H),7.45-7.40(m,3H),7.34(t,J=7.5Hz,1H),7.20(d,J=7.4Hz,1H),2.38(s,3H);13C{1H}NMR(100MHz,DMSO-d6)δ167.0,152.4,141.7,140.8,138.8,137.9,137.3,136.9,136.8,130.1,128.2,127.8,127.3,127.0,126.8,118.9,115.5,21.1;IR(film):2915,2359,1645,1454,1412,1339,1239,767,733cm-1;HRMS(EI)m/z:[M]+CalcdforC18H14O2262.0994;Found262.0994.O2-(p-Tolyl)azulene-1-carboxylicacid(3d):Yield:39.5mg(75%);Rf=OH0.2(Acetone:Hexane=1:4);Bluesolid;Meltingpoint:186-188oC;1HMeNMR(400MHz,DMSO-d6)δ9.39(d,J=9.9Hz,1H),8.62(d,J=9.4Hz,1H),8.03(d,J=8.5Hz,2H),7.94(t,J=9.8Hz,1H),7.74(d,J=8.4Hz,2H),7.66(t,J=9.9Hz,1H),7.59(t,J=9.7Hz,1H),7.51(s,1H),3.90(s,3H);13C{1H}NMR(100MHz,DMSO-d6)δ167.1,152.2,141.7,140.8,138.6,137.7,137.0,136.6,134.4,129.6,128.6,127.3,127.0,118.7,115.3,20.8;IR(film):2361,2341,1631,1451,1437,1413,1345,806cm-1;HRMS(EI)m/z:[M]+CalcdforC18H14O2262.0994;Found262.0992.S5

5O2-(4-Fluorophenyl)azulene-1-carboxylicacid(3e):Yield:40.7mgOH(76%);Rf=0.2(Acetone:Hexane=1:4);Bluesolid;Meltingpoint:225-F227oC;1HNMR(400MHz,CDCl3)δ9.62(d,J=10.0Hz,1H),8.42(d,J=9.5Hz,1H),7.80(t,J=9.8Hz,1H),7.64-7.58(m,3H),7.50(t,J=9.6Hz,1H),7.31(s,1H),7.15(t,J=8.8Hz,2H);13C{1H}NMR(100MHz,acetone-d6)δ167.0,164.6,162.2,153.3,143.5,142.8,139.7,138.6(d,J=34.0Hz),135.3(d,J=3.1Hz),132.7,132.6,128.4(d,J=39.1Hz),120.3,115.5,115.3;19FNMR(376MHz,CDCl3)δ-114.48;IR(film):2359,2341,1647,1417,1223,669,606cm-1;HRMS(EI)m/z:[M]+CalcdforC17H11FO2266.0743;Found266.0742.O2-(3-Chlorophenyl)azulene-1-carboxylicacid(3f):Yield:41.8mg(74%);OHClRo1f=0.2(Acetone:Hexane=1:4);Bluesolid;Meltingpoint:202-204C;HNMR(400MHz,DMSO-d6)δ12.46(s,1H),δ9.39(d,J=10.0Hz,1H),8.60(d,J=9.5Hz,1H),7.93(d,J=9.8Hz,1H),7.68-7.54(m,4H),7.50-7.43(m,3H);13C{1H}NMR(100MHz,DMSO-d6)δ166.6,150.5,141.8,140.8,139.7,139.5,138.6,137.6,132.5,129.7,129.2,128.3,127.7,127.4,127.3,119.2,115.2;IR(film):2922,2360,1638,1455,1338,1241,1093,887,782,691cm-1;HRMS(EI)m/z:[M]+CalcdforC353717H11ClO2282.0448,C17H11ClO2284.0418;Found282.0446,284.0837.O2-(4-Chlorophenyl)azulene-1-carboxylicacid(3g):Yield:44.0mgOH(78%);Rf=0.2(Acetone:Hexane=1:4);Bluesolid;Meltingpoint:216-Cl218oC;1HNMR(400MHz,CDCl3)δ9.63(d,J=10.1Hz,1H),8.45(d,J=9.6Hz,1H),7.82(t,J=9.8Hz,1H),7.65-7.58(m,3H),7.51(t,J=9.8Hz,1H),7.44(d,J=8.4Hz,2H),7.31(s,1H);13C{1H}NMR(100MHz,DMSO-d6)δ166.7,150.9,141.8,140.9,139.3,138.4,137.4,136.4,132.5,131.4,127.89,127.88,127.7,127.4,119.0;IR(film):2360,2341,1641,1439,1412,1345,1240,1098cm-1;HRMS(EI)m/z:[M]+CalcdforC3517H11ClO2282.0448,C3717H11ClO2284.0418;Found282.0450,284.0412.S6

6O2-(2-Bromophenyl)azulene-1-carboxylicacid(3h):Yield:47.2mg(72%);OHRo1f=0.2(Acetone:Hexane=1:4);Bluesolid;Meltingpoint:218-220C;HNMR(400MHz,DMSO-d6)δ9.58(d,J=10.0Hz,1H),8.63(d,J=9.3Hz,Br1H),7.97(t,J=9.8Hz,1H),7.71-7.66(m,2H),7.61(t,J=9.7Hz,1H),7.47-7.38(m,2H),7.34-7.29(m,2H);13C{1H}NMR(100MHz,DMSO-d6)δ166.0,151.9,142.0,140.3,140.1,139.7,138.6,137.8,131.8,130.8,129.0,127.9,127.5,127.0,122.5,119.5,115.7;IR(film):2915,2348,2360,1646,1537,1118,668cm-1;HRMS(EI)m/z:[M]+CalcdforC7917H11BrO2325.9942,C8117H11BrO2327.9922;Found325.9940,327.9923.O2-(4-Chlorophenyl)azulene-1-carboxylicacid(3i):Yield:51.1mgOH(78%);Rf=0.2(Acetone:Hexane=1:4);Bluesolid;Meltingpoint:244-Bro1246C;HNMR(400MHz,DMSO-d6)δ12.40(s,1H),9.35(d,J=9.8Hz,1H),8.58(d,J=9.5Hz,1H),7.90(t,J=9.9Hz,1H),7.65-7.63(m,3H),7.60-7.54(m,3H),7.45(s,1H);13C{1H}NMR(100MHz,DMSO-d6)δ166.7,151.0,141.9,140.9,139.3,138.4,137.4,136.7,131.7,130.8,127.8,127.4,121.2,118.9,115.0;IR(film):2360,2341,1537,1451,1254,1105,750,668cm-1;HRMS(EI)m/z:[M]+CalcdforC798117H11BrO2325.9942,C17H11BrO2327.9922;Found325.9943,327.9931.O2-(4-(Trifluoromethyl)phenyl)azulene-1-carboxylicacid(3j):Yield:OH44.1mg(69%);Rf=0.2(Acetone:Hexane=1:4);Bluesolid;MeltingCF3point:238-240oC;1HNMR(400MHz,CDCl3)δ9.65(d,J=9.8Hz,1H),8.46(d,J=9.2Hz,1H),7.84(t,J=9.4Hz,1H),7.73-7.68(m,4H),7.62(t,J=9.6Hz,1H),7.52(t,J=9.6Hz,1H),7.32(s,1H);13C{1H}NMR(100MHz,DMSO-d6)δ166.5,150.6,141.9,140.9,139.8,138.9,137.9,130.33,130.32,127.9,127.7(q,J=31.8Hz),127.6,124.6(q,J=3.9Hz),19FNMR(376MHz,DMSO-d124.5(q,J=272.0Hz),119.3,115.1;6)δ-60.84;IR(film):2928,2360,1652,1455,1328,1123,1067,808,668cm-1;HRMS(EI)m/z:[M]+CalcdforC18H11F3O2316.0711;Found316.0710.S7

7O2-(4-(Methoxycarbonyl)phenyl)azulene-1-carboxylicacid(3k):OHYield:45.9mg(75%);Rf=0.2(Acetone:Hexane=1:4);Bluesolid;CO2Meo1Meltingpoint:240-242C;HNMR(400MHz,CDCl3)δ9.65(d,J=10.0Hz,1H),8.47(d,J=9.6Hz,1H),8.13(d,J=8.3Hz,2H),7.84(t,J=9.8Hz,1H),7.71(d,J=8.4Hz,2H),7.63(t,J=10.0Hz,1H),7.52(t,J=9.6Hz,1H),7.35(s,1H),3.96(s,3H);13C{1H}NMR(100MHz,DMSO-d6)δ166.6,166.2,150.9,142.5,141.9,140.9,139.7,138.9,137.7,130.0,128.7,128.4,127.9,127.6,119.2,115.2,52.2;IR(film):2923,2361,1715,1649,1454,1281,605cm-1;HRMS(EI)m/z:[M]+CalcdforC19H14O4306.0892;Found306.0892.O2-(Thiophen-2-yl)azulene-1-carboxylicacid(3l):Yield:34.3mg(68%);Rf=OH0.2(Acetone:Hexane=1:4);Bluesolid;Meltingpoint:187-189oC;1HNMRS(400MHz,CDCl3)δ9.46(d,J=10.1Hz,1H),8.33(d,J=9.7Hz,1H),7.74(d,J=3.4Hz,1H),7.69(t,J=9.7Hz,1H),7.51-7.39(m,4H),7.12(s,1H);13C{1H}NMR(100MHz,acetone-d6)δ167.4,145.4,143.1,142.9,140.0,139.2,138.3,137.9,130.4,128.9,128.61,128.60,128.2,119.6,115.3;IR(film):2919,2361,2341,1647,1455,1241,607cm-1;HRMS(EI)m/z:[M]+CalcdforC15H10O2S254.0402;Found254.0401.O2-(2-Bromophenyl)-6-methylazulene-1-carboxylicacid(3m):Yield:OH40.8mg(60%);Rf=0.2(Acetone:Hexane=1:4);redsolid;Meltingpoint:Me233-235oC;1HNMR(400MHz,DMSO-d6)δ11.96(s,1H),9.41(d,J=Br10.5Hz,1H),8.47(d,J=10.1Hz,1H),7.67(dd,J=8.0Hz,J=1.0Hz,1H),7.59(d,J=10.5Hz,1H),7.51(d,J=10.1Hz,1H),7.45-7.36(m,2H),7.31-7.27(m,1H),7.21(s,1H),2.72(s,3H);13C{1H}NMR(100MHz,DMSO-d6)δ166.1,151.8,150.6,140.6,140.2,139.0,137.7,136.9,131.8,130.8,129.3,128.9,128.8,126.9,122.6,119.4,115.6,27.5;IR(film):2739,1772,1638,1454,1265,829,615cm-1;HRMS(EI)m/z:[M]+CalcdforC7918H13BrO2340.0099,C8118H13BrO2342.0079;Found340.0102,342.0072.S8

82-(2-Bromophenyl)-6-phenylazulene-1-carboxylicacid(3n):Yield:OOH44.3mg(55%);Rf=0.2(Acetone:Hexane=1:4);Bluesolid;Meltingpoint:238-240oC;1HNMR(400MHz,DMSO-d6)δ11.85(s,1H),9.61Ph(d,J=10.6Hz,1H),8.65(d,J=10.2Hz,1H),7.90(dd,J=10.6Hz,J=Br1.6Hz,1H),7.83-7.79(m,3H),7.70(d,J=8.0Hz,1H),7.60-7.56(m,2H),7.54-7.50(m,1H),7.47-7.40(m,2H),7.34-7.30(m,2H);13C{1H}NMR(100MHz,DMSO-d6)δ165.5,151.6,151.6,143.2,140.4,139.8,138.8,137.4,136.8,131.5,130.5,128.7,128.5,128.3,128.2,127.4,126.9,126.5,122.2,119.4,116.1;IR(film):3409,2341,2114,1560,1234,669,588cm-1;HRMS(EI)m/z:[M]+CalcdforC798123H15BrO2402.0255,C23H15BrO2404.0235;Found402.0255,404.0244.O2-(2-Bromophenyl)-3-methylazulene-1-carboxylicacid(3o):Yield:36.1OHmg(53%);Rf=0.3(Acetone:Hexane=1:4);Bluesolid;Meltingpoint:220-222oC;1HNMR(400MHz,DMSO-d6)δ11.88(s,1H),9.56(d,J=9.9Hz,MeBr1H),8.57(d,J=9.7Hz,1H),7.91(t,J=9.7Hz,1H),7.72(d,J=7.8Hz,1H),7.62-7.53(m,2H),7.48-7.45(m,1H),7.35-7.27(m,2H),2.28(s,3H);13C{1H}NMR(100MHz,DMSO-d6)δ165.9,151.3,140.0,139.7,139.4,139.4,137.2,135.8,131.7,130.6,128.9,127.2,127.0,126.2,124.2,122.5,114.5,10.6;IR(film):3351,2252,2126,1663,1028,824,761,618cm-1;HRMS(EI)m/z:[M]+CalcdforC798118H13BrO2340.0099,C18H13BrO2342.0079;Found340.0097,342.0083.ProcedurefortheIr-CatalyzedSequentialArylationandCyclizationReactionofAzulene-1-carboxylicAcidswithDiaryliodoniumSaltsOOOH[Cp*IrCl2]2(4.0mol%)OAgOAc(3.0equiv)+IXR3HKOAc(1.0equiv)R3R12oDMF,80C,2hR1R2X=OTf,BF42R124S9

9Adriedtesttubeequippedwithamagneticstirrerwaschargedwithazulene-1-carboxylicacids(1)(0.2mmol),diaryliodoniumsalts(2)(0.24mmol),[Cp*IrCl2]2(4.0mol%,6.4mg),AgOAc(3.0equiv,100.2mg),KOAc(1.0equiv,19.7mg),andDMF(1.0mL)underanitrogenatmosphere.Afterbeingstirredat80°Cfor2h,thereactionmixturewascooledtoroomtemperature,filteredthroughapadofCelite,andconcentratedunderreducedpressure.Thecrudeproductwaspurifiedbycolumnchromatographyonsilicagel.Procedureforscale-upreactionAdriedtesttubeequippedwithamagneticstirrerwaschargedwithazulene-1-carboxylicacid(1a)(1.0mmol,172.2mg),diphenyliodoniumtriflate(2a)(1.2mmol,516.2mg),[Cp*IrCl2]2(4.0mol%,31.9mg),AgOAc(3.0equiv,500.7mg),KOAc(1.0equiv,98.2mg),andDMF(5.0mL)underanitrogenatmosphere.Afterbeingstirredat80°Cfor2h,thereactionmixturewascooledtoroomtemperature,filteredthroughapadofCelite,andconcentratedunderreducedpressure.Thefiltratewasconcentratedunderreducedpressure,andtheresiduewaspurifiedbysilicagelfreshcolumnchromatography(Acetone:Hexane=1:4)togive4a(214.3mg,87%).3-Phenyl-1H-azuleno[1,8-bc]furan-1-one(4a):Yield:43.3mg(88%);Rf=OO0.4(Acetone:Hexane=1:4);Redsolid;Meltingpoint:106-108oC;1HNMR(400MHz,CDCl3)δ8.37-8.32(m,3H),7.94(t,J=10.4Hz,1H),7.63-7.58(m,2H),7.55-7.48(m,3H),7.45-7.41(m,1H);13C{1H}NMR(100MHz,CDCl3)δ163.0,156.8,148.6,145.1,138.3,137.5,137.4,134.1,129.9,129.2,128.6,128.4,117.3,113.9,110.2;IR(film):3060,2360,1760,1633,1495,1348,1219,1104,756,668cm-1;HRMS(EI)m/z:[M]+CalcdforC17H10O2246.0681;Found246.0684.3-(o-Tolyl)-azuleno[1,8-bc]furan-1-one(4b):Yield:36.4mg(70%);Rf=0.4OOMe(Acetone:Hexane=1:4);Redsolid;Meltingpoint:125-127oC;1HNMR(400MHz,CDCl3)δ8.40(d,J=9.4Hz,1H),7.98(t,J=10.4Hz,1H),7.86-7.84(m,1H),7.63(t,J=10.1Hz,1H),7.50(d,J=9.9Hz,1H),7.37-7.32(m,4H),2.61(s,3H);13C{1H}NMR(100MHz,CDCl3)δ162.5,157.3,149.1,144.3,138.6,137.8,137.2,136.9,134.3,131.3,131.3,129.1,128.2,126.3,121.7,113.7,112.0,21.2;IR(film):2359,2340,1769,S10

101634,1496,1455,1337,1219,756cm-1;HRMS(EI)m/z:[M]+CalcdforC18H12O2260.0837;Found260.0834.O3-(m-Tolyl)-1H-azuleno[1,8-bc]furan-1-one(4c):Yield:37.5mg(72%);OMeo1Rf=0.4(Acetone:Hexane=1:4);Redsolid;Meltingpoint:181-183C;HNMR(400MHz,CDCl3)δ8.31(d,J=9.4Hz,1H),8.15-8.12(m,2H),7.90(t,J=10.4Hz,1H),7.59-7.54(m,2H),7.45(d,J=9.9Hz,1H),7.41(t,J=7.6Hz,1H),7.24(d,J=7.6Hz,1H),2.47(s,3H);13C{1H}NMR(100MHz,CDCl3)δ163.1,156.8,149.0,145.2,138.8,138.2,137.6,137.4,134.1,130.9,129.19,129.16,128.3,126.0,117.3,113.9,110.4,21.7;IR(film):2363,1759,1634,1490,1389,1218,741cm-1;HRMS(EI)m/z:[M]+CalcdforC18H14O2260.0837;Found260.0836.O3-(p-Tolyl)-1H-azuleno[1,8-bc]furan-1-one(4d):Yield:37.5mg(72%);ORof=0.4(Acetone:Hexane=1:4);Redsolid;Meltingpoint:186-188C;Me1HNMR(400MHz,CDCl3)δ8.25(d,J=9.4Hz,1H),8.18(d,J=8.1Hz,2H),7.84(t,J=10.3Hz,1H),7.54-7.49(m,2H),7.39(d,J=9.9Hz,1H),7.29(d,J=8.0Hz,2H),2.41(s,3H);13C{1H}NMR(100MHz,CDCl3)δ163.1,156.5,148.9,145.1,140.4,137.8,137.6,137.1,131.5,129.9,128.6,128.3,116.8,113.9,110.2,21.7;IR(film):2916,1758,1635,1496,1455,1341,1218,802,772,739cm-1;HRMS(EI)m/z:[M]+CalcdforC18H12O2260.0837;Found260.0839.O3-(3-Chlorophenyl)-1H-azuleno[1,8-bc]furan-1-one(4e):Yield:29.2mgOCl(52%);Rf=0.4(Acetone:Hexane=1:4);Redsolid;Meltingpoint:184-186oC;1HNMR(400MHz,CDCl3)δ8.39(d,J=9.4Hz,1H),8.30-8.27(m,1H),8.25-8.24(m,1H),7.99(t,J=10.4Hz,1H),7.66-7.60(m,2H),7.51(d,J=9.9Hz,1H),7.46(t,J=7.8Hz,1H),7.40-7.38(m,1H);13C{1H}NMR(100MHz,DMSO-d6)δ166.0,151.9,142.0,140.3,140.1,139.7,138.6,137.8,131.8,130.8,129.0,127.9,127.5,127.0,122.5,119.5,115.7;IR(film):2915,2359,1768,1537,1455,1106,741cm-1;HRMS(EI)m/z:[M]+CalcdforC353717H9ClO2280.0291,C17H9ClO2282.0261;Found280.0289,282.0340.S11

11OO3-(4-Chlorophenyl)-1H-azuleno[1,8-bc]furan-1-one(4f):Yield:42.8mg(76%);Rf=0.4(Acetone:Hexane=1:4);Redsolid;Meltingpoint:Cl173-175oC;1HNMR(400MHz,CDCl3)δ8.32(d,J=9.3Hz,1H),8.20(d,J=6.8Hz,2H),7.92(t,J=10.3Hz,1H),7.58(t,J=10.0Hz,1H),7.51(s,1H),7.46-7.42(m,3H);13C{1H}NMR(100MHz,CDCl3)δ162.9,157.0,147.1,145.1,138.6,137.7,137.5,135.8,132.6,129.8,129.4,128.6,117.3,114.1,110.2;IR(film):2359,2341,1780,1635,1495,1113,1093,539cm-1;HRMS(EI)m/z:[M]+CalcdforC353717H9ClO2280.0291,C17H9ClO2282.0261;Found280.0291,282.0273.O3-(4-Bromophenyl)-1H-azuleno[1,8-bc]furan-1-one(4g):Yield:50.6Omg(78%);Rf=0.4(Acetone:Hexane=1:4);Redsolid;Meltingpoint:Br199-201oC;1HNMR(400MHz,CDCl3)δ8.34(d,J=9.4Hz,1H),8.14(d,J=8.4Hz,2H),7.94(t,J=10.4Hz,1H),7.62-7.57(m,3H),7.53(s,1H),7.46(d,J=9.9Hz,1H);13C{1H}NMR(100MHz,CDCl3)δ162.9,157.1,147.2,145.1,138.7,137.8,137.5,133.0,132.4,130.0,128.6,124.3,117.4,114.2,110.2;IR(film):2926,2360,1755,1635,1493,1460,1336,1262,1103,801cm-1;HRMS(EI)m/z:[M]+CalcdforC798117H9BrO2323.9786,C17H9BrO2325.9766;Found323.9788,325.9782.O3-(Thiophen-2-yl)-1H-azuleno[1,8-bc]furan-1-one(4h):Yield:32.9mgOo(65%);Rf=0.4(Acetone:Hexane=1:4);Redsolid;Meltingpoint:115-117C;S1HNMR(400MHz,CDCl3)δ8.26-8.24(m,2H),7.87(t,J=10.4Hz,1H),7.56(t,J=10.1Hz,1H),7.46-7.44(m,2H),7.34-7.32(m,1H),7.20-7.18(m,1H);13C{1H}NMR(100MHz,DMSO-d6)δ161.8,155.7,144.1,139.6,139.5,138.4,137.6,137.4,130.2,130.1,129.9,129.1,117.0,115.1,107.7;IR(film):2918,2360,1763,1628,1498,1338,1098,566cm-1;HRMS(EI)m/z:[M]+CalcdforC15H8O2S252.0245;Found252.0246.S12

12O7-Methyl-3-phenyl-1H-azuleno[1,8-bc]furan-1-one(4i):Yield:37.4Omg(72%);Rf=0.4(Acetone:Hexane=1:4);Redsolid;Meltingpoint:Me184-186oC;1HNMR(400MHz,CDCl3)δ8.29(d,J=7.6Hz,2H),8.18(d,J=9.9Hz,1H),7.53-7.49(m,4H),7.42-7.38(m,2H),2.83(s,3H);13C{1H}NMR(100MHz,CDCl3)δ163.2,156.1,151.6,147.5,144.3,136.5,136.1,134.4,130.1,129.7,129.2,128.5,117.3,115.5,110.0,29.9;IR(film):2928,2362,1768,1644,1496,828,754cm-1;HRMS(EI)m/z:[M]+CalcdforC18H12O2260.0837;Found260.0836.O3,7-Diphenyl-1H-azuleno[1,8-bc]furan-1-one(4j):Yield:41.2mgO(64%);Rf=0.4(Acetone:Hexane=1:4);Redsolid;Meltingpoint:195-Ph197oC;1HNMR(400MHz,CDCl3)δ8.35-8.31(m,3H),7.78(d,J=10.0Hz,1H),7.64-7.62(m,3H),7.58(s,1H),7.55-7.50(m,5H),7.44-7.40(m,1H);13C{1H}NMR(100MHz,CDCl3)δ163.2,155.9,153.2,148.5,144.9,144.4,136.6,136.3,134.3,129.9,129.7,129.3,129.2,129.0,128.9,128.6,117.5,114.7,110.5;IR(film):2915,2360,1770,1638,1498,691,512cm-1;HRMS(EI)m/z:[M]+CalcdforC23H14O2322.0994;Found322.0996.O4-Methyl-3-phenyl-1H-azuleno[1,8-bc]furan-1-one(4k):Yield:40.1mgO(77%);Rf=0.4(Acetone:Hexane=1:4);Redsolid;Meltingpoint:198-200oC;1HNMR(400MHz,CDCl3)δ8.37(d,J=9.4Hz,1H),7.99(d,J=7.3MeHz,2H),7.93(t,J=10.3Hz,1H),7.61-7.53(m,3H),7.45-7.41(m,2H),2.74(s,3H);13C{1H}NMR(100MHz,CDCl3)δ163.0,156.9,145.2,143.7,138.3,137.6,135.7,134.6,130.0,128.9,128.8,128.2,127.1,113.0,110.7,12.7;IR(film):2914,2359,1759,1631,1501,748,-1;HRMS(EI)m/z:[M]+CalcdforC606cm18H12O2260.0837;Found260.0840.ProcedurefortheIr-CatalyzedCyclizationof2-Phenylazulene-1-carboxylicAcidS13

13OOOH[Cp*IrCl2]2(4.0mol%)OAgOAc(3.0equiv)KOAc(1.0equiv)oDMF,80C,12h3a4aAdriedtesttubeequippedwithamagneticstirrerwaschargedwith2-phenylazulene-1-carboxylicacid(3a)(0.2mmol,34.5mg),[Cp*IrCl2]2(4.0mol%,6.4mg),AgOAc(3.0equiv,100.2mg),KOAc(1.0equiv,19.7mg),andDMF(1.0mL)underanitrogenatmosphere.Afterbeingstirredat80°Cfor12h,thereactionmixturewascooledtoroomtemperature,filteredthroughapadofCelite,andconcentratedunderreducedpressure.Thefiltratewasconcentratedunderreducedpressure,andtheresiduewaspurifiedbysilicagelfreshcolumnchromatography(Acetone:Hexane=1:4)togive4a(39.4mg,80%).ProcedurefortheIr-CatalyzedDiarylationReactionofAzulene-2-carboxylicAcidwithDiphenyliodoniumSalt[Cp*IrCl2]2(4.0mol%)HPhAgOAc(1.0equiv)OO+Na2HPO4(1.0equiv)Ph2IOTfoOHDMF,80C,2hOHHPh5a2a6aAdriedtesttubeequippedwithamagneticstirrerwaschargedwithazulene-2-carboxylicacids(5a)(0.2mmol),diphenyliodoniumtriflate(2a)(0.4mmol),[Cp*IrCl2]2(4.0mol%,6.4mg),AgOAc(1.0equiv,33.4mg),Na2HPO4(1.0equiv,28.4mg),andDMF(1.0mL)underanitrogenatmosphere.Afterbeingstirredat80°Cfor2h,thereactionmixturewascooledtoroomtemperature,filteredthroughapadofCelite,andconcentratedunderreducedpressure.Thefiltratewasconcentratedunderreducedpressure,andtheresiduewaspurifiedbysilicagelfreshcolumnchromatography(Acetone/CH2Cl2=1:7)togive6a(33.7mg,52%).Ph1,3-Diphenylazulene-2-carboxylicAcid(6a):Yield:33.7mg(52%);Rf=0.5O(Acetone/CHo12Cl2=1:7);Bluesolid;Meltingpoint:112-114C;HNMR(400OHMHz,CDCl3)δ8.32(d,J=9.4Hz,2H),7.61(t,J=9.8Hz,1H),7.50-7.44(m,Ph8H),7.41-7.37(m,2H),7.10(t,J=9.9Hz,2H);13C{1H}NMR(100MHz,S14

14CDCl3)δ171.1,141.1,139.8,137.2,135.8,135.5,131.0,130.3,128.4,127.3,124.3;IR(film):3413,3052,2922,1688,1433,1266,701cm-1;HRMS(EI)m/z:[M]+CalcdforC23H16O2324.1150;Found324.1151.3.StudiesontheKineticIsotopeEffectOO[Cp*IrCl2]2(4.0mol%)OOHOHNaHPOOH24(1.0equiv)AgOAc(1.0equiv)HorD+PhI2OTfoPhDMF,60C,2hHDH/D1a1a-[D2]2a3a-[D(3)]1aor1a-[D2]kineticmeasurementKH/KD=2.421aor1a-[D2]parallelreactionsKH/KD=2.221a+1a-[D2]intermolecularcompetitionKH/KD=2.70KineticMeasurementByusing1a(0.10mmol)or1a-[D2](0.10mmol)assubstrate,aseriesofreactionswerecarriedoutintwoseparatedreactiontubesunderstandardconditionsfordifferenttime.ThereactionmixturewasmeasuredforNMRanalysisusingdibromomethaneasaninternalstandard.TheKIEwascalculatedbytheslopsoftwolines:Time(min)0101520303a(%)051117203a-[D(3)](%)02789KIE=2.42S15

1525y=0.72x-0.220153a(%)10y=0.298x+3.36293a-[D(3)](%)ProductYield(%)5005101520253035Time(min)ParallelReactionsByusing1a(20.7mg,0.12mmol)and1a-[D2](20.9mg,0.12mmol)assubstrate,respectively,parallelreactionswerecarriedoutintwoseparatedreactiontubesunderstandardconditionsfor30min.Theirreactionmixtureswerecombinedforpurification.Products3aand3a-[D(3)]wereobtainedasamixtureandtheirratiowasdeterminedbyNMR.IntermolecularCompetitionToatesttubewereaddedazulene-1-carboxylicacid(1a),azulene-1-carboxylicacid(1a-[D2]),diphenyliodoniumtriflate(2a),[Cp*IrCl2]2,AgOAc,Na2HPO4,andDMF.Theresultingmixturewasstirredat60oC(bathtemperature)for2h.AfterCelitefiltrationandevaporationofthesolventinvacuo,thecrudeproductwaspurifiedbycolumnchromatographyonsilicagel(acetone:hexane=1:3)to3a+3a-[D(3)](48%)asabluesolid.4.X-rayCrystallographyX-raycrystallographyof4a4a(10.0mg)wasdissolvedinDCM(1.0mL)ina4mLglassvialtogiveaclearsolution.Thissolutionwasaddedto10mLglassvialcontainingn-hexane(5mL).The10mLvialwassealedwithS16

16ascrewcap.Vapordiffusionaffordedcrystalsofthecomposition4asuitableforX-raydiffractionwithin2dayatroomtemperature.Ablock-likespecimenofC17H10O2,approximatedimensions0.132x0.124x0.098mm3,wasusedfortheX-raycrystallographicanalysis.TheX-rayintensitydataweremeasured.(ellipsoid=30%,CCDC=1944899)TableS3.Crystaldataandstructurerefinementfor4a.EmpiricalformulaC17H10O2Formulaweight246.25Temperature173(2)KWavelength0.71073ÅCrystalsystemMonoclinicSpacegroupP21/nUnitcelldimensionsa=13.696(3)Åα=90°b=9.272(2)Åβ=105.625(7)°c=19.496(5)Åγ=90°Volume2384.2(10)Å3Z8S17

17Density(calculated)1.372Mg/m3Absorptioncoefficient0.090mm-1F(000)1024Crystalsize0.132x0.124x0.098mm3Thetarangefordatacollection3.048to25.998°.Indexranges−16<=h<=16,−11<=k<=11,−24<=l<=24Reflectionscollected33785Independentreflections4682[R(int)=0.1749]Completenesstotheta=25.242°99.8%AbsorptioncorrectionSemi-empiricalfromequivalentsMax.andmin.transmission0.7454and0.6698RefinementmethodFull-matrixleast-squaresonF2Data/restraints/parameters4682/0/343Goodness-of-fitonF21.126FinalRindices[I>2sigma(I)]R1=0.1367,wR2=0.2379Rindices(alldata)R1=0.2139,wR2=0.2722Largestdiff.peakandhole0.683and−0.280e·Å−3S18

185.References(1)(a)Fujinaga,M.;Suetake,K.;Gyoji,K.;Murafuji,T.;Kurotobi,K.;Sugihara,Y.AnEasyAccessto2-SubstitutedAzulenesfromAzulene-2-boronicAcidPinacolEster.Synthesis2008,23,3745-3748.(b)Narita,M.;Murafuji,T.;Yamashita,S.;Fujinaga,M.;Hiyama,K.;Oka,Y.;Tani,F.;Kamijo,S.;Ishiguro,K.Synthesisof2-IodoazulenesbytheIododeboronationofAzulen-2-ylboronicAcidPinacolEsterswithCopper(I)Iodide.J.Org.Chem.2018,83,1298-1303.(c)Sigrist,R.;Hansen,H.-J.ReportonanUnusualCascadeReactionbetweenAzulenesand2,3-Dichloro-5,6-dicyano-1,4-benzoquinone(=4,5-Dichloro-3,6-dioxocyclohexa-1,4-diene-1,2-dicar-bonitrile;DDQ).Helv.Chim.Acta2010,93,1545-1567.(d)Maeng,C.;Son,J.-Y.;Lee,S.C.;Baek,Y.;Um,K.;Han,S.H.;Ko,G.H.;Han,G.U.;Lee,K.;Lee,K.;Lee,P.H.ExpansionofAzulenesasNonbenzenoidAromaticCompoundsforC−HActivation:Rhodium-andIridium-CatalyzedOxidativeCyclizationofAzuleneCarboxylicAcidswithAlkynesfortheSynthesisofAzulenolactonesandBenzoazulenes.J.Org.Chem.2020,85,3824-3837.(2)(a)Merritt,E.A.;Malmgren,J.;Klinke,F.J.;Olofsson,B.SynthesisofDiaryliodoniumTriflatesUsingEnvironmentallyBenignOxidizingAgents.Synlett2009,2009,2277-2280;(b)Zhu,M.;Jalalian,N.;Olofsson,B.One-potsynthesisofdiaryliodoniumsaltsusingtoluenesulfonicacid:afastentrytoelectron-richdiaryliodoniumtosylatesandtriflates.Synlett2008,2008,592-596;(c)Bielawski,M.;Aili,D.;Olofsson,B.Regiospecificone-potsynthesisofdiaryliodoniumtetrafluoroboratesfromarylboronicacidsandaryliodides.J.Org.Chem.2008,73,4602-4607;S19

196.1H,13C,and19FNMRdataS20

202-Phenylazulene-1-carboxylicacid(3a)1HNMR(400MHz,CDCl3)9.639.608.448.427.817.787.687.667.617.597.567.507.487.477.457.427.417.397.347.26OOHPh3a1.0001.0141.1402.1231.2174.2041.0381110987654321ppm

212-Phenylazulene-1-carboxylicacid(3a)13CNMR(100MHz,CDCl3)170.0154.9143.6143.3138.7138.2137.9137.8130.0128.7128.1127.9127.8120.5113.177.577.276.8OOHPh3a2001901801701601501401301201101009080706050403020100ppm

222-(o-Tolyl)azulene-1-carboxylicacid(3b)1HNMR(400MHz,CDCl3)9.719.698.458.437.857.827.807.657.627.607.537.517.497.337.337.327.317.317.297.297.287.277.277.267.212.20-0.00OOHMe3b1.0241.0001.0111.0331.0454.1341.0163.2031110987654321ppm

232-(o-Tolyl)azulene-1-carboxylicacid(3b)13CNMR(100MHz,DMSO-d6)166.4153.6142.1140.7139.1138.8138.0137.2135.2129.3129.0127.8127.4127.1125.0119.6115.840.139.939.739.539.339.138.920.0OOHMe3b2001901801701601501401301201101009080706050403020100ppm

242-(m-Tolyl)azulene-1-carboxylicacid(3c)1HNMR(400MHz,DMSO-d6)9.289.268.578.547.897.877.857.627.607.577.557.537.517.457.447.417.397.367.347.327.217.192.522.522.512.512.502.38OOHMe3c1.0241.0251.0311.0391.0583.0531.0351.0363.0001110987654321ppm

252-(m-Tolyl)azulene-1-carboxylicacid(3c)13CNMR(100MHz,DMSO-d6)167.0152.4141.7140.8138.8137.9137.3136.9136.8130.1128.2127.8127.3127.0126.8118.9115.540.139.939.739.539.339.138.921.1OOHMe3c2001901801701601501401301201101009080706050403020100ppm

262-(p-Tolyl)azulene-1-carboxylicacid(3d)1HNMR(400MHz,DMSO-d6)9.409.388.648.618.048.027.967.947.927.757.737.687.667.637.617.597.567.513.902.522.512.512.512.50OOHMe3d1.0001.0162.0451.0522.0531.0781.0481.0313.0591110987654321ppm

272-(p-Tolyl)azulene-1-carboxylicacid(3d)13CNMR(100MHz,DMSO-d6)167.1152.2141.7140.8138.6137.7137.0136.6134.4129.6128.6127.3127.0118.7115.340.139.939.739.539.339.138.920.8OOHMe3d2001901801701601501401301201101009080706050403020100ppm

282-(4-Fluorophenyl)azulene-1-carboxylicacid(3e)1HNMR(400MHz,CDCl3)9.639.608.448.427.837.807.787.647.647.637.627.617.617.587.527.507.487.317.267.177.157.130.00OOHF3e1.0191.0491.0473.0071.1481.0362.2311110987654321ppm

292-(4-Fluorophenyl)azulene-1-carboxylicacid(3e)13CNMR(100MHz,acetone-d6)206.1167.0164.6162.2153.3143.5142.8139.7138.8138.5135.3135.3132.7132.6128.6128.2120.3115.6115.5115.330.430.230.029.829.629.529.3OOHF3e2001901801701601501401301201101009080706050403020100ppm

302-(4-Fluorophenyl)azulene-1-carboxylicacid(3e)19FNMR(376MHz,CDCl3)-114.48OOHF3e0-20-40-60-80-100-120-140-160-180ppm

312-(3-Chlorophenyl)azulene-1-carboxylicacid(3f)1HNMR(400MHz,DMSO-d6)12.469.409.388.618.587.957.937.907.687.657.637.607.587.577.577.567.557.557.547.507.487.467.467.457.447.447.432.522.512.512.502.50OOHCl3f1.0391.0001.0411.1004.0833.111121110987654321ppm

322-(3-Chlorophenyl)azulene-1-carboxylicacid(3f)13CNMR(100MHz,DMSO-d6)166.6150.5141.8140.8139.7139.5138.6137.6132.5129.7129.2128.3127.7127.4127.3119.2115.240.239.939.739.539.339.138.9OOHCl3f2001901801701601501401301201101009080706050403020100ppm

332-(4-Chlorophenyl)azulene-1-carboxylicacid(3g)1HNMR(400MHz,CDCl3)9.649.628.468.447.857.827.807.657.637.607.587.547.517.497.457.427.317.26-0.00OOHCl3g1.0001.0061.0513.2501.2942.0901.0831110987654321ppm

342-(4-Chlorophenyl)azulene-1-carboxylicacid(3g)13CNMR(100MHz,DMSO-d6)166.7150.9141.8140.9139.3138.4137.4136.4132.5131.4127.9127.9127.7127.4119.039.939.739.539.339.1OOHCl3g2001901801701601501401301201101009080706050403020100ppm

352-(2-Bromophenyl)azulene-1-carboxylicacid(3h)1HNMR(400MHz,DMSO-d6)9.599.568.648.627.997.977.947.717.707.707.697.687.687.667.637.617.597.477.467.457.457.437.437.417.407.397.387.347.337.327.317.307.292.522.512.512.502.501.15OOHBr3h1.0001.0161.0182.0331.0512.0672.0091110987654321ppm

362-(2-Bromophenyl)azulene-1-carboxylicacid(3h)13CNMR(100MHz,DMSO-d6)166.0151.9142.0140.3140.1139.7138.6137.8131.8130.8129.0127.9127.5127.0122.5119.5115.740.139.939.739.539.339.138.9OOHBr3h2001901801701601501401301201101009080706050403020100ppm

372-(4-Chlorophenyl)azulene-1-carboxylicacid(3i)1HNMR(400MHz,DMSO-d6)12.409.369.338.608.577.937.907.887.657.647.637.637.607.587.567.547.452.512.512.502.502.49OOHBr3i1.0641.0001.0491.0883.0063.0741.000121110987654321ppm

382-(4-Chlorophenyl)azulene-1-carboxylicacid(3i)13CNMR(100MHz,DMSO-d6)166.7151.0141.9140.9139.3138.4137.4136.7131.7130.8127.8127.4121.2118.9115.040.139.939.739.539.339.138.9OOHBr3i2001901801701601501401301201101009080706050403020100ppm

392-(4-(Trifluoromethyl)phenyl)azulene-1-carboxylicacid(3j)1HNMR(400MHz,CDCl3)9.669.638.478.457.857.837.817.737.717.697.687.657.627.607.547.527.497.327.250.00OOHCF33j1.0001.0051.0224.0351.1061.1201.0011110987654321ppm

402-(4-(Trifluoromethyl)phenyl)azulene-1-carboxylicacid(3j)13CNMR(100MHz,DMSO-d6)166.5150.6141.9140.9139.8138.9137.9130.3130.3128.5128.2127.9127.9127.6127.6127.3125.8124.7124.6124.6124.6123.1120.4119.3115.140.139.939.739.539.339.138.9OOHCF33j2001901801701601501401301201101009080706050403020100ppm

412-(4-(Trifluoromethyl)phenyl)azulene-1-carboxylicacid(3j)19FNMR(376MHz,DMSO-d6)-60.84OOHCF33j-5-10-15-20-25-30-35-40-45-50-55-60-65-70-75-80-85-90ppm

422-(4-(Methoxycarbonyl)phenyl)azulene-1-carboxylicacid(3k)1HNMR(400MHz,CDCl3)9.669.638.488.458.148.127.867.847.817.727.707.667.637.617.557.527.507.357.263.96-0.00OOHCO2Me3k1.0001.0511.9931.0572.0121.0831.0891.0353.0141110987654321ppm

432-(4-(Methoxycarbonyl)phenyl)azulene-1-carboxylicacid(3k)13CNMR(100MHz,DMSO-d6)166.6166.2150.9142.5141.9140.9139.7138.9137.7130.0128.7128.4127.9127.6119.2115.252.240.139.939.739.539.339.138.9OOHCO2Me3k2001901801701601501401301201101009080706050403020100ppm

442-(Thiophen-2-yl)azulene-1-carboxylicacid(3l)1HNMR(400MHz,CDCl3)9.479.458.358.327.747.737.717.697.667.517.497.467.447.437.417.397.267.120.00OOHS3l1.0001.0131.0111.1004.0061.0221110987654321ppm

452-(Thiophen-2-yl)azulene-1-carboxylicacid(3l)1HNMR(100MHz,acetone-d6)206.1167.4145.4143.1142.9140.0139.2138.3137.9130.4128.9128.6128.6128.2119.6115.330.430.230.029.829.629.529.3OOHS3l2102001901801701601501401301201101009080706050403020100ppm

462-(2-Bromophenyl)-6-methylazulene-1-carboxylicacid(3m)1HNMR(400MHz,DMSO-d6)11.969.429.398.488.457.687.687.667.667.607.587.527.507.447.447.427.427.417.407.387.387.367.367.317.317.297.297.297.297.277.277.212.722.512.502.502.502.49OOHMeBr3m1.0001.0861.0621.1281.1061.0712.2811.1271.0413.190121110987654321ppm

472-(2-Bromophenyl)-6-methylazulene-1-carboxylicacid(3m)13CNMR(100MHz,DMSO-d6)166.1151.8150.6140.6140.2139.0137.7136.9131.8130.8129.3128.9128.8126.9122.6119.4115.640.139.939.739.539.339.138.927.5OOHMeBr3m2001901801701601501401301201101009080706050403020100ppm

482-(2-Bromophenyl)-6-phenylazulene-1-carboxylicacid(3n)1HNMR(400MHz,DMSO-d6)11.859.629.598.668.637.927.927.897.897.837.827.817.817.797.717.697.607.607.587.567.547.527.527.507.477.477.457.447.437.427.427.417.407.347.337.327.307.302.522.512.512.512.50OOHPhBr3n1.0311.0001.0111.0533.0391.1482.0021.1742.0712.072121110987654321ppm

492-(2-Bromophenyl)-6-phenylazulene-1-carboxylicacid(3n)13CNMR(100MHz,DMSO-d6)165.5151.6151.6143.2140.4139.8138.8137.4136.8131.5130.5128.7128.5128.3128.2127.4126.9126.5122.2119.4116.140.139.939.739.539.339.138.9OOHPhBr3n2001901801701601501401301201101009080706050403020100ppm

502-(2-Bromophenyl)-3-methylazulene-1-carboxylicacid(3o)1HNMR(400MHz,DMSO-d6)11.889.569.538.578.557.937.907.887.727.707.617.587.577.567.547.527.477.457.437.347.337.327.307.307.287.287.267.262.512.502.502.502.492.27OOHMeBr3o1.0001.1111.1221.1651.1242.0571.1912.1683.167121110987654321ppm

512-(2-Bromophenyl)-3-methylazulene-1-carboxylicacid(3o)13CNMR(100MHz,DMSO-d6)165.9151.3140.0139.7139.4139.4137.2135.8131.7130.6128.9127.2127.0126.2124.2122.5114.540.139.939.739.539.339.138.910.6OOHMeBr3o2001901801701601501401301201101009080706050403020100ppm

523-Phenyl-1H-azuleno[1,8-bc]furan-1-one(4a)1HNMR(400MHz,CDCl3)8.378.358.358.348.338.327.977.947.927.637.627.607.607.587.557.547.537.527.517.517.507.487.457.457.457.437.437.437.417.417.417.26-0.00OO4a3.0711.0002.0713.0291.0051110987654321ppm

533-Phenyl-1H-azuleno[1,8-bc]furan-1-one(4a)13CNMR(100MHz,CDCl3)163.0156.8148.6145.1138.3137.5137.4134.1129.9129.2128.6128.4117.3113.9110.277.577.276.8OO4a2001901801701601501401301201101009080706050403020100ppm

543-(o-Tolyl)-azuleno[1,8-bc]furan-1-one(4b)1HNMR(400MHz,CDCl3)8.418.388.017.987.967.867.867.857.847.847.657.637.607.517.497.377.357.347.347.337.327.252.61-0.00OOMe4b1.0001.0441.0111.0451.0224.1103.1441110987654321ppm

553-(o-Tolyl)-azuleno[1,8-bc]furan-1-one(4b)13CNMR(100MHz,CDCl3)162.5157.3149.1144.3138.6137.8137.2136.9134.3131.3131.3129.1128.2126.3121.7113.7112.077.577.276.821.2OOMe4b2001901801701601501401301201101009080706050403020100ppm

563-(m-Tolyl)-1H-azuleno[1,8-bc]furan-1-one(4c)1HNMR(400MHz,CDCl3)8.338.308.158.127.927.907.877.597.577.577.547.467.447.437.417.397.267.257.232.47-0.00OOMe4c1.0462.0001.0422.1341.0871.0961.0153.1111110987654321ppm

573-(m-Tolyl)-1H-azuleno[1,8-bc]furan-1-one(4c)13CNMR(100MHz,CDCl3)163.1156.8149.0145.2138.8138.2137.6137.4134.1130.9129.2129.2128.3126.0117.3113.9110.477.577.276.821.7OOMe4c2001901801701601501401301201101009080706050403020100ppm

583-(p-Tolyl)-1H-azuleno[1,8-bc]furan-1-one(4d)1HNMR(400MHz,CDCl3)8.268.248.198.177.867.847.817.547.527.497.407.387.307.287.252.41-0.00OOMe4d1.0772.0001.0342.2061.0392.0413.2091110987654321ppm

593-(p-Tolyl)-1H-azuleno[1,8-bc]furan-1-one(4d)1HNMR(100MHz,CDCl3)163.1156.5148.9145.1140.4137.8137.6137.1131.5129.9128.6128.3116.8113.9110.277.577.276.821.7OOMe4d2001901801701601501401301201101009080706050403020100ppm

603-(3-Chlorophenyl)-1H-azuleno[1,8-bc]furan-1-one(4e)1HNMR(400MHz,CDCl3)8.408.388.308.308.288.278.248.248.248.017.997.967.667.637.637.607.527.507.487.467.447.407.407.407.407.387.387.387.26-0.00OOCl4e1.0001.0171.0201.0062.1031.0411.0641.0771110987654321ppm

613-(3-Chlorophenyl)-1H-azuleno[1,8-bc]furan-1-one(4e)13CNMR(100MHz,DMSO-d6)166.0151.9142.0140.3140.1139.7138.6137.8131.8130.8129.0127.9127.5127.0122.5119.5115.740.139.939.739.539.339.138.9OOCl4e2001901801701601501401301201101009080706050403020100ppm

623-(4-Chlorophenyl)-1H-azuleno[1,8-bc]furan-1-one(4f)1HNMR(400MHz,CDCl3)8.338.318.218.197.957.927.907.617.587.567.517.467.447.427.26-0.00OOCl4f1.0112.0241.0001.0811.0713.0411110987654321ppm

633-(4-Chlorophenyl)-1H-azuleno[1,8-bc]furan-1-one(4f)13CNMR(100MHz,CDCl3)162.9157.0147.1145.1138.6137.7137.5135.8132.6129.8129.4128.6117.3114.1110.277.577.276.8OOCl4f2001901801701601501401301201101009080706050403020100ppm

643-(4-Bromophenyl)-1H-azuleno[1,8-bc]furan-1-one(4g)1HNMR(400MHz,CDCl3)8.358.338.158.137.977.947.927.627.617.597.577.537.477.457.26-0.00OOBr4g1.0262.0621.0363.0311.0291.0001110987654321ppm

653-(4-Bromophenyl)-1H-azuleno[1,8-bc]furan-1-one(4g)13CNMR(100MHz,CDCl3)162.9157.1147.2145.1138.7137.8137.5133.0132.4130.0128.6124.3117.4114.2110.277.577.276.8OOBr4g2001901801701601501401301201101009080706050403020100ppm

663-(Thiophen-2-yl)-1H-azuleno[1,8-bc]furan-1-one(4h)1HNMR(400MHz,CDCl3)8.278.268.258.247.907.877.847.587.557.537.477.467.457.447.347.337.327.267.217.207.197.180.00OOS4h2.0401.0701.0732.0431.0771.0001110987654321ppm

673-(Thiophen-2-yl)-1H-azuleno[1,8-bc]furan-1-one(4h)13CNMR(100MHz,DMSO-d6)161.8155.7144.1139.6139.5138.4137.6137.4130.2130.1129.9129.1117.0115.1107.740.139.939.739.539.339.138.9OOS4h2001901801701601501401301201101009080706050403020100ppm

687-Methyl-3-phenyl-1H-azuleno[1,8-bc]furan-1-one(4i)1HNMR(400MHz,CDCl3)8.308.288.198.177.537.527.517.497.427.407.387.262.830.00OOMe4i2.0191.0004.2692.1253.1841110987654321ppm

697-Methyl-3-phenyl-1H-azuleno[1,8-bc]furan-1-one(4i)13CNMR(100MHz,CDCl3)163.2156.1151.6147.5144.3136.5136.1134.4130.1129.7129.2128.5117.3115.5110.077.577.276.829.9OOMe4i2001901801701601501401301201101009080706050403020100ppm

703,7-Diphenyl-1H-azuleno[1,8-bc]furan-1-one(4j)1HNMR(400MHz,CDCl3)8.358.338.317.797.777.647.627.587.557.537.517.507.447.427.407.260.00OOPh4j3.0001.0493.0341.0315.0841.0041110987654321ppm

713,7-Diphenyl-1H-azuleno[1,8-bc]furan-1-one(4j)1HNMR(100MHz,CDCl3)163.2155.9153.2148.5144.9144.4136.6136.3134.3129.9129.7129.3129.2129.0128.9128.6117.5114.7110.577.577.276.8OOPh4j2001901801701601501401301201101009080706050403020100ppm

724-Methyl-3-phenyl-1H-azuleno[1,8-bc]furan-1-one(4k)1HNMR(400MHz,CDCl3)8.388.358.007.987.967.937.917.617.587.577.557.537.457.437.417.262.740.00OOMe4k1.0072.0001.0303.1702.0853.0561110987654321ppm

734-Methyl-3-phenyl-1H-azuleno[1,8-bc]furan-1-one(4k)13CNMR(100MHz,CDCl3)163.0156.9145.2143.7138.3137.6135.7134.6130.0128.9128.8128.2127.1113.0110.777.577.276.812.7OOMe4k2001901801701601501401301201101009080706050403020100ppm

741,3-Diphenylazulene-2-carboxylicAcid(6a)1HNMR(400MHz,CDCl3)8.338.317.637.617.587.507.507.497.487.487.467.457.447.417.417.407.407.397.387.377.257.127.107.07-0.00PhOOHPh6a2.0001.1258.0552.0782.0081110987654321ppm

751,3-Diphenylazulene-2-carboxylicAcid(6a)13CNMR(100MHz,CDCl3)171.1141.1139.8137.2135.8135.5131.0130.3128.4127.3124.377.577.276.8PhOOHPh6a2001901801701601501401301201101009080706050403020100ppm

76Azulene-1-carboxylicacids(1a-[D2])1HNMR(400MHz,CDCl3)9.739.718.528.508.487.897.867.847.657.647.637.617.607.547.527.497.357.347.26-0.00H(100%),D(0%)OH/DOHHa/DH(20%),D(80%)1a-[D]Ha1.0001.0880.2031.1811.1961.1831.1071110987654321ppm

772-Phenylazulene-1-carboxylicacid(3a-[D2])1HNMR(400MHz,CDCl3)9.629.608.448.427.817.797.767.677.677.657.657.617.607.597.587.567.517.487.467.467.447.427.427.417.407.397.347.26-0.00H(70%),D(30%)OHa/DOHPhH/DH(100%),D(0%)3a-[D(8)]Ha0.7011.0001.0592.0041.0874.1221.0131110987654321ppm

782-Phenylazulene-1-carboxylicacid(3a-[D1])1HNMR(400MHz,CDCl3)9.629.598.458.427.817.797.777.677.667.667.657.647.627.597.577.517.487.487.487.467.447.437.427.427.417.407.347.26-0.00OOHPhHa/DH(73%),D(27%)3a-[D(3)]Ha1.0001.0011.1472.1621.1984.3550.7351110987654321ppm