and Meldrum ’ s Acid Derivatives - Brosge et al. - Unknown - Unknown

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S1SupportingInformationfor5-Carbonyl-1,3-oxazine-2,4-dionesfromN-CyanosulfoximinesandMeldrum’sAcidDerivatives†††‡‡FelixBrosge,JohannesFlorianKochs,MarielaBregu,Khai-NghiTruong,KariRissanen,and,†CarstenBolm*†InstituteofOrganicChemistry,RWTHAachenUniversity,Landoltweg1,52074Aachen,Germany‡DepartmentofChemistry,UniversityofJyvaskyla,P.O.Box35,Survontie9B,40014Jyväskylä,FinlandE-mail:Carsten.Bolm@oc.rwth-aachen.deTableofContentSectionPage1.GeneralinformationS22.Chemicalsynthesesandanalyticaldataofstartingmaterials3and8S23.Chemicalsynthesesandanalyticaldataofproducts13S64.NMRspectraS125.SingleCrystalX-raystructureof13aaS416.ReferencesS42

1S21.GeneralinformationUnlessotherwisestated,allreactionswerecarriedoutunderambientatmosphereandmagneticstirring.Liquidsandsolutionsweretransferredviasyringes.AnhydroussolventsweretakenfromanMBRAUNsolventpurificationsystemorpurchasedfromcommercialsuppliersasextradrysolventsovermolecularsievesinsealedbottles.N-Cyanosulfoximines3andMeldrum’sacidderivatives81,2werepreparedusingconventionalproceduresknownintheliterature(section2).Allotherreagentswereobtainedfromcommercialsuppliersandusedwithoutfurtherpurification.Oilbathswereusedasheatingsourcesforallreactionsthatrequiredelevatedtemperatures.Thereactionprogresswasmonitoredbythinlayerchromatography(TLC)withaluminiumsheetssilicagel60F254fromMerckanddetectionofthecompoundswithanUVlamp(λ=254nmand365nm).Flashcolumnchromatography(FCC)purificationswereperformedonAcrosOrganicssilicagel60A(35-70µm)usingstandardtechniques.Nuclearmagneticresonance(NMR)spectrawererecordedatroomtemperatureinCDCl3or(CD3)2SOonAgilentVNMRS600,AgilentVNMRS400,BrukerAvanceNeo400orBrukerAvance600.Chemicalshifts(δ)aregiveninpartspermillion(ppm)relativetothe1131residualsolventpeaks[CDCl3:HNMRδ=7.26ppm;CNMRδ=77.16ppm;(CD3)2SO:HNMR13δ=2.50ppm;CNMRδ=39.52ppm].Couplingconstants(J)arereportedinHz.Multiplicitiesareabbreviatedbys(singlet),d(doublet),dd(doubletofdoublet),t(triplet),tt(tripletoftriplet),q(quartet),br(broad)andm(multiplet).Mass(MS)spectraweremeasuredonaFinniganSSQ7000spectrometer(EI,70eV).Highresolutionmass(HRMS)spectrawererecordedusingelectrosprayionization(ESI)onaThermoScientificLTQOrbitrapXLspectrometerwithOrbitrapmassanalyzeroraBrukermaXisIIspectrometerwithTOFmassanalyzer.Theatomicmassofthemolecularionandthefragmentsperelementarycharge(m/z)arereportedindimensionlessquantities.Infrared(IR)spectrawererecordedwithaPerkinElmer100FT/IRspectrometerwithanattachedUATRdevice–1DiamondKRS-5.Wavenumbers(ν)oftheabsorptionbandsaregivenincm.Meltingpoints(mp)weremeasuredwithopen-endcapillariesonaBüchiB-540meltingpointmachine.2.Chemicalsynthesesandanalyticaldataofstartingmaterials3and8SynthesesofN-cyanosulfoximines3N-Cyanosulfoximines3weresynthesizedinoneortwostepsfromthecorrespondingsulfidesorsulfoxidesinanalogytoliteraturereportedprotocolandrecordedNMRdataareinfullagreementwith1thepublishedanalyticaldata.6N-[Methyl(oxo)(phenyl)-λ-sulfanylidene]cyanamide(3a)1Followingaliteraturereportedprotocol,3awasobtainedfrom(methylsulfinyl)benzene(10.0g,71.3mmol,1.0equiv),cyanamide(5.99g,144mmol,2.0equiv),potassiumtert-butoxide(16.2g,144mmol,2.0equiv)andN-chlorosuccinimide(19.2g,144mmol,2.0equiv)asacolorlesssolid(11.1g,161.6mmol,86%)afterFCC(pentane:EtOAc–1:1).HNMR(400MHz,CDCl3):δ=8.09–7.92(m,1312H),7.85–7.75(m,1H),7.73–7.62(m,2H),3.34(s,3H)ppm;C{H}NMR(101MHz,CDCl3):δ=136.2,135.6,130.4,128.0,111.9,44.9ppm.6N-[Cyclopropyl(oxo)(phenyl)-λ-sulfanylidene]cyanamide(3b)1Followingaliteraturereportedprotocol,3bwasobtainedfromcyclopropylphenylsulfide(0.430mL,3.00mmol,1.0equiv),sodiumperiodate(706mg,3.30mmol,1.1equiv),cyanamide(252mg,6.00mmol,2.0equiv),potassiumtert-butoxide(673mg,6.00mmol,2.0equiv),andN-chlorosuccinimide(801mg,6.00mmol,2.0equiv)asacolorlessliquid(213mg,1.03mmol,34%)afterFCC(pentane:EtOAc–2:1to1:1).

2S31HNMR(400MHz,CDCl3):δ=8.01–7.90(m,2H),7.81–7.72(m,1H),7.71–7.60(m,2H),2.83–1312.57(m,1H),1.80–1.65(m,1H),1.45–1.27(m,2H),1.20–1.05(m,1H)ppm;C{H}NMR(101MHz,CDCl3):δ=136.6,135.2,130.2,128.1,112.2,33.8,7.2,6.1ppm.6N-[(4-Bromophenyl)(methyl)(oxo)-λ-sulfanylidene]cyanamide(3c)1Followingaliteraturereportedprotocol,3cwasobtainedfrom4-bromothioanisole(609mg,3.00mmol,1.0equiv),sodiumperiodate(706mg,3.30mmol,1.1equiv),cyanamide(252mg,6.00mmol,2.0equiv)potassiumtert-butoxide(673mg,6.00mmol,2.0equiv)andN-chlorosuccinimide(801mg,6.00mmol,2.0equiv)as1acolorlesssolid(263mg,1.01mmol,34%)afterFCC(pentane:EtOAc–2:1to1:1).HNMR131(600MHz,CDCl3):δ=7.91–7.76(m,4H),3.34(s,3H)ppm;C{H}NMR(151MHz,CDCl3):δ=135.1,133.8,131.5,129.5,111.5,44.9ppm.6N-[Methyl(4-nitrophenyl)(oxo)-λ-sulfanylidene]cyanamide(3d)1Followingaliteraturereportedprotocol,3dwasobtainedfrom1-(methyl-sulfinyl)-4-nitrobenzene(1.85g,10.0mmol,1.0equiv),cyanamide(1.26g,30.0mmol,3.0equiv),potassiumtert-butoxide(3.36g,30.0mmol,3.0equiv)andN-chlorosuccinimide(4.01g,30.0mmol,3.0equiv)asapaleyellowsolid1(427mg,1.90mmol,19%)afterFCC(pentane:EtOAc–2:3to100%EtOAc).HNMR(600MHz,131CDCl3):δ=8.55–8.51(m,2H),8.26–8.21(m,2H),3.42(s,3H)ppm;C{H}NMR(151MHz,CDCl3):δ=151.9,142.0,129.8,125.5,110.8,44.7ppm.6N-[(4-Formylphenyl)(methyl)(oxo)-λ-sulfanylidene]cyanamide(3e)1Followingaliteraturereportedprotocol,3ewasobtainedfrom4-(methylsulfinyl)benzaldehyde(2.24g,13.3mmol,1.0equiv),cyanamide(1.12g,26.7mmol,2.0equiv),potassiumtert-butoxide(2.98g,26.7mmol,2.0equiv)andN-chlorosuccinimide(3.55g,26.7mmol,2.0equiv)asawhitesolid(179mg,10.860mmol,6%)afterFCC(pentane:EtOAc–2:3to1:4).HNMR(600MHz,CDCl3):δ=10.17131(s,1H),8.22–8.15(m,4H),3.40(s,3H)ppm;C{H}NMR(151MHz,CDCl3):δ=190.2,141.1,140.9,131.1,129.0,111.3,44.7ppm.6N-[Cyclohexyl(methyl)(oxo)-λ-sulfaneylidene]cyanamide(3f)1Followingaliteraturereportedprotocol,3fwasobtainedfrom(methylsulfinyl)cyclohexane(1.65g,11.3mmol,1.0equiv),cyanamide(950mg,22.6mmol,2.0equiv),potassiumtert-butoxide(2.54g,22.6mmol,2.0equiv)andN-chlorosuccinimide(3.02g,22.6mmol,2.0equiv)asacolorlessoil(483mg,2.59mmol,23%)after1FCC(pentane:EtOAc–3:2to2:3).HNMR(600MHz,CDCl3):δ=3.26–3.18(m,1H),3.13(s,3H),2.33–2.22(m,2H),2.10–1.94(m,2H),1.85–1.73(m,1H),1.64–1.53(m,2H),1.42–1.32(m,1312H),1.29–1.19(m,1H)ppm;C{H}NMR(151MHz,CDCl3):δ=112.6,64.4,37.0,25.6,25.5,25.1,25.1,24.8ppm.6N-[(4-Methoxyphenyl)(methyl)(oxo)-λ-sulfanylidene]cyanamide(3g)1Followingaliteraturereportedprotocol,3gwasobtainedfrom1-methoxy-4-(methylsulfinyl)benzene(1.48g,8.69mmol,1.0equiv),cyanamide(735mg,17.4mmol,2.0equiv),potassiumtert-butoxide(1.95g,17.4mmol,2.0equiv)andN-chlorosuccinimide(2.32g,17.4mmol,2.0equiv)asacolorlesssolid(1.42g,16.78mmol,79%)afterFCC(pentane:EtOAc–2:1to1:2).HNMR(600MHz,CDCl3):δ=7.98–1317.83(m,2H),7.14–7.08(m,2H),3.92(s,3H),3.31(s,3H)ppm;C{H}NMR(151MHz,CDCl3):δ=165.3,130.4,126.7,115.6,112.27,56.1,45.4ppm.

3S46N-(Oxodiphenyl-λ-sulfaneylidene)cyanamide(3h)1Followingaliteraturereportedprotocol,3hwasobtainedfromsulfinyldibenzene(2.78g,13.7mmol,1.0equiv),cyanamide(1.45g,34.5mmol,2.5equiv),potassiumtert-butoxide(3.86g,34.4mmol,2.5equiv)andN-chlorosuccinimide(4.59g,34.4mmol,2.5equiv)asacolorlesssolid(522mg,2.15mmol,16%)afterFCC1(pentane:EtOAc–3:1to2:1).HNMR(600MHz,CDCl3):δ=8.05–7.95(m,4H),7.72–7.66(m,1312H),7.64–7.56(m,4H)ppm;C{H}NMR(151MHz,CDCl3):δ=137.4,134.9,130.2,128.0,112.1ppm.6N-[(4-Acetylphenyl)(methyl)(oxo)-λ-sulfanylidene]cyanamide(3i)1Followingaliteraturereportedprotocol,3iwasobtainedfrom1-[4-(methylsulfinyl)phenyl]ethan-1-one(1.71g,9.39mmol,1.0equiv),cyanamide(789mg,18.8mmol,2.0equiv),potassiumtert-butoxide(2.11g,18.8mmol,2.0equiv)andN-chlorosuccinimide(2.51g,18.8mmol,2.0equiv)asacolorless1solid(1.27g,5.73mmol,61%)afterFCC(pentane:EtOAc–2:1to1:2).HNMR(600MHz,131CDCl3):δ=8.24–8.18(m,2H),8.14–8.08(m,2H),3.38(s,3H),2.69(s,3H)ppm;C{H}NMR(151MHz,CDCl3):δ=196.3,142.3,139.9,130.0,128.6,111.4,44.7,27.1ppm.SynthesesofsubstitutedMeldrum’sacids8Except8e,allsubstitutedMeldrum’sacids8weresynthesizedunderargonatmosphereinonestepfromthecorrespondingacylchlorideinanalogytoliteraturereportedprotocolandtherecordedNMR2,33dataareinwiththepublishedanalyticaldata.Becausefor8enoanalyticaldatawereprovided,thecompoundwasfullycharacterizedhere.5-(1-Hydroxyethylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione(8a)2Followingaliteraturereportedprotocol,8awasobtainedfromMeldrum’sacid(10.0g,69.4mmol,1.0equiv),acylchloride(5.94mL,83.3mmol,1.2equiv)andpyridine(11.3mL,139mmol,2.0equiv)asabrownsolidafterrecrystallisationfromEtOAc1(8mL)coatedwithpentane(40mL)at–20°C(9.36g,50.3mmol,72%).HNMR131(600MHz,CDCl3):δ=15.12(br,1H),2.68(s,3H),1.73(s,6H)ppm;C{H}NMR(151MHz,CDCl3):δ=194.8,170.3,160.6,105.1,92.0,27.0,23.7ppm.5-(1-Hydroxy-2-phenylethylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione(8b)2Followingaliteraturereportedprotocol,8bwasobtainedfromMeldrum’sacid(3.00g,20.8mmol,1.0equiv),phenylacetylchloride(4.13mL,31.2mmol,1.5equiv)andDMAP(5.09g,41.6mmol,2.0equiv)asabrownsolidafterrecrystallisationfromEtOAc(7mL)1coatedwithpentane(35mL)at–20°C(4.08g,15.5mmol,75%).HNMR(600MHz,CDCl3):δ=15.31(br,1H),7.38–7.35(m,2H),7.33–7.29(m,2H),7.29–7.25(m,1H),1314.41(s,2H),1.70(s,6H)ppm;C{H}NMR(151MHz,CDCl3):δ=194.8,170.6,160.5,134.2,129.8,128.9,127.7,105.1,91.6,41.0,27.0ppm.

4S55-[Hydroxy(phenyl)methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione(8c)2Followingaliteraturereportedprotocol,8cwasobtainedfromMeldrum’sacid(1.00g,6.94mmol,1.0equiv),benzoylchloride(1.04mL,9.02mmol,1.3equiv)andDMAP(1.70g,13.9mmol,2.0equiv)asayellowsolidafterrecrystallizationfromEtOAc1(4mL)at–20°C(1.09g,6.01mmol,87%).HNMR(600MHz,CDCl3):δ=15.47(br,1H),7.70–7.66(m,2H),7.63–7.58(m,1H),7.49–7.45(m,2H),1.85(s,6H)ppm;131C{H}NMR(151MHz,CDCl3):δ=189.4,171.1,160.0,133.5,132.8,129.6,128.2,105.2,91.1,27.0ppm.5-[Hydroxy(4-methoxyphenyl)methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione(8d)2Followingaliteraturereportedprotocol,8dwasobtainedfromMeldrum’sacid(1.50g,10.4mmol,1.0equiv),4-methoxybenzoylchloride(2.18mL,15.6mmol,1.5equiv)andDMAP(2.54g,20.8mmol,2.0equiv)asayellowsolidafter1recrystallizationfromacetone(15mL)at–20°C(1.42g,5.10mmol,49%).HNMR(600MHz,CDCl3):δ=15.48(br,1H),7.79–7.66(m,2H),7.01–6.86(m,1312H),3.88(s,3H),1.84(s,6H)ppm;C{H}NMR(151MHz,CDCl3):δ=188.3,171.3,164.4,160.6,132.6,124.6,113.6,104.8,89.7,55.7,26.8ppm.5-[(4-Bromophenyl)(hydroxy)methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione(8e)2Followingaliteraturereportedprotocol,8ewasobtainedfromMeldrum’sacid(1.50g,10.4mmol,1.0equiv),4-bromobenzoylchloride(3.43g,15.6mmol,1.5equiv)andDMAP(2.54g,20.8mmol,2.0equiv)asayellowsolidafterrecrystallizationfromacetone(15mL)at–20°C(2.65g,8.11mmol,78%).Mp:97–198°C;HNMR(600MHz,CDCl3):δ=15.54(br,1H),7.63–7.58(m,2H),7.57–1317.53(m,2H),1.84(s,6H)ppm;C{H}NMR(151MHz,CDCl3):δ=188.2,171.1,159.9,131.6,131.1,128.6,105.3,91.2,27.0ppm.IR(ATR)ν=3814,3458,3318,3095,3006,2944,2660,2547,2325,2067,1925,1786,1734,1653,1581,1542,1476,1385,1271,1204,1137,1066,–1+1031,1007,933,903,864,834,799,722,680cm;MS(EI)m/z:328(20)[M+H],326(21),226(24),224(24),185(100),183(100),157(22),155(22),76(11),75(10);MS(CI)m/z:234(28),232(18),225(50),218(11),184(29),173(19),163(12),157(24),156(100),141(80),127(13),125(42),123(10),118(13),111(40),109(10),102(58),101(21),100(29),83(11),74(20),72(10),65+(21);HRMS(ESI)m/z:[M+Na]CalcdforC13H11O5NaBr348.9682;Found:348.9685.5-[Hydroxy(4-nitrophenyl)methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione(8f)2Followingaliteraturereportedprotocol,8fwasobtainedfromMeldrum’sacid(1.50g,10.4mmol,1.0equiv),4-nitrobenzoylchloride(2.89g,15.6mmol,1.5equiv)andDMAP(2.54g,20.8mmol,2.0equiv)asayellowsolidafterrecrystallizationfromacetone(15mL)at–20°C(1.60g,5.47mmol,53%;ca.85%puritywithby-productsstemmingfromhydrolysisanddecarboxylationofthe1productasalsoobservedandreportedinref.3).HNMR(600MHz,CDCl3):δ=13115.59(br,1H),8.33–8.30(m,2H),7.96–7.61(m,2H),1.85(s,6H)ppm;C{H}NMR(151MHz,CDCl3):δ=186.8,170.8,159.4,150.1,138.7,130.4,123.4,105.9,92.3,27.1ppm.

5S63.Chemicalsynthesesandanalyticaldataofproducts13TableS1:Screeningofthereactionconditions(withsulfoximine3aandMeldrum'sacid8aasastartingmaterials)HHOR3ONOONCN+OOOO1S2tolueneRROOONMe120°C,2hSMeMeR1R238(4.0equiv)13EntrySolventTemperature(°C)Equivof8aYieldof13aa(%)1Toluene801752Toluene802873Toluene803914Toluene804945Toluene1001676Toluene1002877Toluene1003958Toluene1004769Toluene12016710Toluene12028711Toluene120385b12Toluene12049913DCM5012414DCM5023415DCM5033516DCM5044217MeCN9016818MeCN9026319MeCN9036720MeCN90471aReactionconditions:3ainsolvent(0.5M),heatingfor2h;yieldsdeterminedbyNMRwithdimethylsulfoneasinternalstandard(exceptentry12);b)aftercolumnchromatography.3.1Generalprocedureforthesynthesisofsulfoximines13(GP1)Ascrewcapvialequippedwithmagneticstirringbarwaschargedwithsulfoximine3(1.0equiv),toluene(0.5M)andthecorrespondingMeldrum’sacidderivative8(4.0equiv).Theresultingsuspensionwasstirredat120°Cfor2h.Aftercompletionofthereaction,thereactionmixturewascooledtoambienttemperature,andwaterwassubsequentlyadded.ThecrudemixturewasextractedwithDCM(4x).ThecombinedorganiclayersweredriedoveranhydrousMgSO4,andthesolventswereremovedunderreducedpressurebyarotaryevaporator.PurificationbyFCCusingn-pentane/ethylacetate(1:1to1:2ratiosolution)affordedsulfoximines13.

6S766-Methyl-N-[methyl(oxo)(phenyl)-λ-sulfanylidene]-2,4-dioxo-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13aa)FollowingGP1,13aawassynthesizedfrom3a(90.1mg,0.500mmol,1equiv)and8a(372mg,2.00mmol,4equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasawhitesolid(153mg,0.496mmol,99%).Thisreactionwasalsoperformedona4.03mmolscaleproviding13aain90%yield1(1.12g).Mp:182–183°C;HNMR(600MHz,(CD3)2SO):δ=11.95(s,1H),8.08–8.02(m,2H),7.80–7.76(m,1H),7.71(m,2H),3.54(s,3H),2.20(s,3H)131ppm;C{H}NMR(151MHz,(CD3)2SO):δ=169.4,164.6,160.3,147.1,137.8,134.0,129.6,127.2,113.7,43.2,17.5ppm;IR(ATR)ν=3537,3159,3034,2919,2846,2348,2166,2105,2033,1975,1910,1781,1687,1620,1447,1411,1324,1281,1217,1168,1110,1007,970,928,892,825,–1785,740,683cm;MS(EI)m/z:274(23),208(11),183(11),182(100),156(78),153(14),141(10),140(17),125(18),97(10),94(44),93(13),91(19),85(37),83(57),77(27),65(13),51(11),47(13);MS(CI)m/z:198(13),156(23),141(24),103(11),101(18),87(13),85(74),83(100);+HRMS(ESI)m/z:[M+H]CalcdforC13H13O5N2S309.0540;Found:309.0537.66-Benzyl-N-[methyl(oxo)(phenyl)-λ-sulfanylidene]-2,4-dioxo-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13ab)FollowingGP1,13abwassynthesizedfrom3a(180mg,1.00mmol,1equiv)and8b(1.05g,4.00mmol,4equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasabrownsolid(331mg,0.863mmol,86%).Mp:1196–197°C;HNMR(600MHz,(CD3)2SO):δ=12.05(s,1H),8.08–8.02(m,2H),7.82–7.75(m,1H),7.73–7.64(m,2H),7.36–7.24(m,5H),3.87(s,2H),1313.58(s,3H)ppm;C{H}NMR(151MHz,(CD3)2SO):δ=169.3,164.6,160.4,147.1,137.7,134.7,134.0,129.6,129.1,128.7,127.2,114.3,59.8,14.1ppm;IR(ATR)ν=3559,3157,3061,3021,2925,2834,2323,2166,2055,2010,1955,1781,1698,1657,1592,1493,1444,1401,1333,1294,–11230,1184,1151,1101,1030,973,928,877,825,791,744,696cm;MS(EI)m/z:182(19),156(12),118(22),97(10),93(10),92(24),91(93),89(13),78(11),77(100),69(11),65(97),63(26),51(89),45(11);MS(CI)m/z:137(33),119(16),103(14),101(22),91(22),87(11),85(68),83+(100);HRMS(ESI)m/z:[M+Na]CalcdforC19H16O5N2NaS407.0672;Found:407.0666.6N-[Methyl(oxo)(phenyl)-λ-sulfanylidene]-2,4-dioxo-6-phenyl-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13ac)FollowingGP1,13acwassynthesizedfrom3a(90.1mg,0.500mmol,1equiv)and8c(496mg,2.00mmol,4equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasawhitesolid(83.9mg,0.227mmol,45%).Mp:216–1217°C;HNMR(600MHz,(CD3)2SO):δ=12.17(s,1H),7.87–7.83(m,2H),7.79–7.74(m,1H),7.72–7.69(m,2H),7.68–7.63(m,2H),7.61–7.57(m,1H),1317.55–7.48(m,2H),3.47(s,3H)ppm;C{H}NMR(151MHz,(CD3)2SO):δ=169.4,161.1,159.5,147.0,137.6,133.9,131.8,129.9,129.5,128.8,127.8,127.1,113.7,42.9ppm;IR(ATR)ν=3953,3750,3533,3160,3037,2928,2855,2587,2359,2168,2096,–2022,1977,1792,1687,1612,1449,1404,1336,1291,1220,1101,982,909,874,818,771,688cm1;MS(EI)m/z:292(25),291(100),182(94),156(26),140(16),105(42),94(11),77(53),54(19),+48(13);MS(CI)m/z:294(10),293(100);HRMS(ESI)m/z:[M+Na]CalcdforC18H14O5N2NaS393.0516;Found:393.0516.

7S866-(4-Methoxyphenyl)-N-[methyl(oxo)(phenyl)-λ-sulfanylidene]-2,4-dioxo-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13ad)FollowingGP1,13adwassynthesizedfrom3a(90.1mg,0.500mmol,1equiv)and8d(557mg,2.00mmol,4equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasayellowsolid(56.8mg,0.142mmol,28%).Mp:1241–242°C;HNMR(600MHz,(CD3)2SO):δ=12.10(s,1H),7.95–7.88(m,2H),7.80–7.74(m,1H),7.70–7.62(m,4H),7.09–7.00(m,2H),3.84(s,3H),1313.49(s,3H)ppm;C{H}NMR(151MHz,(CD3)2SO):δ=169.9,162.0,161.3,159.1,147.1,137.6,134.0,129.7,129.5,127.2,121.8,114.3,112.2,55.6,42.9ppm;IR(ATR)ν=3141,3010,2921,2841,2323,2161,2059,2001,1887,1778,1676,1599,1509,1448,1404,1337,1310,1264,1223,1177,1121,1095,1023,970,911,878,821,771,745,–1688,666cm;MS(EI)m/z:357(27),342(18),245(10),217(15),183(10),182(100),135(18);MS+(CI)m/z:157(16),156(58),141(27),89(100),61(35);HRMS(ESI)m/z:[M+Na]CalcdforC19H16O6N2NaS423.0621;Found:423.0620.66-(4-Bromophenyl)-N-[methyl(oxo)(phenyl)-λ-sulfanylidene]-2,4-dioxo-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13ae)FollowingGP1,13aewassynthesizedfrom3a(90.1mg,0.500mmol,1.0equiv)and8e(654mg,2.00mmol,4.0equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasayellowsolid(111mg,0.248mmol,50%).Mp:215–1216°C;HNMR(600MHz,(CD3)2SO):δ=12.19(s,1H),7.89–7.83(m,2H),7.82–7.74(m,1H),7.74–7.69(m,2H),7.69–7.63(m,2H),7.63–7.59(m,2H),1313.49(s,3H)ppm;C{H}NMR(151MHz,(CD3)2SO):δ=169.2,161.0,158.6,146.8,137.5,134.0,131.9,129.8,129.5,129.2,127.1,125.5,114.0,42.9ppm;IR(ATR)ν=3747,3515,3232,3172,3064,3022,2926,2832,2556,2390,2306,2260,2178,2105,2059,2002,1978,1906,1784,1699,1629,1588,1486,1386,1329,1280,1219,1095,973,910,872,–1828787,745,684,656cm;MS(EI)m/z:449(10),447(12),185(43),183(46),182(100),157(18),156(38),155(20),140(19),125(14),97(11),94(15),92(11),91(24),85(54),83(77),77(25),76(11),75(10),66(10),59(10),55(12),54(16),53(14),52(31),49(30);MS(CI)m/z:184(14),182+(47),157(15),156(100),141(36),140(14);HRMS(ESI)m/z:[M+Na]CalcdforC18H13O5N2BrNaS470.9621;Found:470.9612.6N-[Methyl(oxo)(phenyl)-λ-sulfanylidene]-6-(4-nitrophenyl)-2,4-dioxo-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13af)FollowingGP1,13afwassynthesizedfrom3a(90.1mg,0.500mmol,1.0equiv)and8f(587mg,2.00mmol,4.0equiv;ca.85%purity).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasayellowsolid(99.2mg,0.2391mmol,48%).Mp:220–221°C;HNMR(600MHz,(CD3)2SO):δ=12.28(s,1H),8.40–8.26(m,2H),7.97–7.91(m,1H),7.90–7.84(m,2H),7.81–7.72(m,1311H),7.67–7.61(m,2H),3.50(s,3H)ppm;C{H}NMR(151MHz,(CD3)2SO):δ=168.9,160.9,157.7,148.9,146.7,137.4,136.0,134.0,129.5,129.4,127.1,123.8,115.3,42.7ppm;IR(ATR)ν=3852,3180,3078,3028,2928,2856,2671,2302,2247,2192,2083,2042,1978,1797,1701,1628,1600,1530,1398,1346,1279,1208,1099,982,914,858,824,783,750,717,686,–1658cm;MS(EI)m/z:182(100),156(18),150(14),140(14),125(14),104(12),77(27),76(12);MS(CI)m/z:184(13),182(21),157(22),156(100),138(14),89(42),61(35);HRMS(ESI)m/z:+[M+Na]CalcdforC18H13O7N3NaS438.0366;Found:438.0359.

8S96N-[Cyclopropyl(oxo)(phenyl)-λ-sulfanylidene]-6-methyl-2,4-dioxo-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13ba)FollowingGP1,13bawassynthesizedfrom3b(81.5mg,0.395mmol,1.0equiv)and8a(283mg,1.52mmol,4.0equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasayellowsolid(115mg,0.344mmol,87%).Mp:183–1184°C;HNMR(400MHz,(CD3)2SO):δ=11.94(s,1H),8.06–7.95(m,2H),7.80–7.74(m,1H),7.73–7.66(m,2H),3.12–3.00(m,1H),2.19(s,3H),1.45–1.33131(m,1H),1.28–1.11(m,2H),1.11–0.99(m,1H)ppm;C{H}NMR(101MHz,(CD3)2SO):δ=169.2,165.2,160.3,147.0,137.9,133.8,129.7,127.3,113.5,32.7,17.5,6.3,4.7ppm;IR(ATR)ν=3854,3747,3382,3249,3162,3066,2929,2834,2578,2479,2308,2222,2164,2129,2102,2044,1998,1904,1780,1687,1624,1435,1406,1311,1288,1216,1163,–11109,1004,888,837,782,749,716,682,658cm;MS(EI)m/z:208(45),182(37),134(16),133(100),125(83),97(18),89(34),77(30),51(12);MS(CI)m/z:363(13),336(16),335(90)[M+++H],293(18),292(100),208(54),182(36),167(20);HRMS(ESI)m/z:[M+Na]CalcdforC15H14O5N2NaS357.0516;Found:357.0511.6N-[(4-Bromophenyl)(methyl)(oxo)-λ-sulfanylidene]-6-methyl-2,4-dioxo-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13ca)FollowingGP1,13cawassynthesizedfrom3c(130mg,0.500mmol,1.0equiv)and8a(372mg,2.00mmol,4.0equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasayellowsolid(110mg,10.284mmol,57%).Mp:189–190°C;HNMR(600MHz,(CD3)2SO):δ=13111.96(s,1H),8.15–7.64(m,4H),3.56(s,3H),2.20(s,3H)ppm;C{H}NMR(151MHz,(CD3)2SO):δ=169.5,164.8,160.3,147.06,137.2,132.6,129.3,128.1,113.5,43.0,17.5ppm;IR(ATR)ν=3859,3385,3162,3058,2996,2915,2850,2638,2536,2305,2241,2213,2164,2126,2088,2046,2001,1953,1910,1836,1773,1697,1621,1572,–11445,1406,1325,1276,1223,1165,1115,1009,978,957,898,831,787,754,718,666cm;MS(EI)m/z:263(10),262(97),261(11),260(100),236(48),234(51),220(19),218(19),205(27),203(28),174(26),173(43),172(88),171(52),170(66),169(10),157(30),155(30),153(21),145(14),143(16),110(11),96(10),91(16),76(27),75(27),74(13),63(18),50(17);MS(CI)m/z:389(38)+·+·[M+2],387(36)M,346(30),344(25),309(14),264(11),262(37),260(27),236(71),234(67),226(13),221(16),219(17),184(14),171(52),159(14),157(25),156(100),155(10),154(12),141+(35),128(32),127(16),102(11),85(22);HRMS(ESI)m/z:[M+Na]CalcdforC13H11O5N2BrNaS408.9464;Found:408.9462.6-Methyl-N-[methyl(4-nitrophenyl)(oxo)-l6-sulfanylidene]-2,4-dioxo-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13da)FollowingGP1,13dawassynthesizedfrom3d(113mg,0.500mmol,1.0equiv)and8a(372mg,2.00mmol,4.0equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasayellowsolid(104mg,10.294mmol,59%).Mp:181–182°C;HNMR(600MHz,(CD3)2SO):δ=11.99(s,1H),8.62–8.46(m,2H),8.39–8.23(m,2H),3.64(s,3H),2.20(s,1313H)ppm;C{H}NMR(151MHz,(CD3)2SO):δ=169.6,165.0,160.2,150.6,147.0,143.7,129.2,124.7,113.2,42.6,17.6ppm;IR(ATR)ν=3427,3168,3100,3011,2928,2807,2376,2257,2163,2046,1933,1831,1767,1705,1630,1530,1400,–11353,1315,1284,1222,1170,1111,989,897,824,749,666cm;MS(EI)m/z:398(15),228(12),227(100),201(31),197(13),186(10),185(90),181(25),170(17),153(17),139(17),99(10),91(13),84(12);MS(CI)m/z:229(11),202(11),201(100),171(46),156(14),128(42),102(15);+HRMS(ESI)m/z:[M+Na]CalcdforC13H11O7N3NaS376.0210;Found:376.0222.

9S106N-[(4-Methoxyphenyl)(methyl)(oxo)-λ-sulfanylidene]-6-methyl-2,4-dioxo-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13ea)FollowingGP1,13eawassynthesizedfrom3e(105mg,0.500mmol,1.0equiv)and8a(372mg,2.00mmol,4.0equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasayellowsolid(88.2mg,10.261mmol,52%).Mp:195–196°C;HNMR(600MHz,(CD3)2SO):δ=11.93(s,1H),8.09–7.81(m,2H),7.32–7.09(m,2H),3.88(s,3H),3.50(s,1313H),2.20(s,3H)ppm;C{H}NMR(151MHz,(CD3)2SO):δ=169.3,164.5,163.4,160.3,147.1,129.5,128.8,114.8,113.8,55.9,43.7,17.5ppm;IR(ATR)ν=3850,3235,3110,3019,2930,2847,2679,2501,2304,2223,2184,2160,2095,2049,2025,1982,1953,1833,1768,1702,1628,1588,1497,1398,1316,1288,1253,1216,1167,1113,1007,977,930,898,–1826,777,663cm;MS(EI)m/z:212(46),186(13),155(36),124(16),123(100);MS(CI)m/z:339+(14)[M+H],297(16),296(100),270(15),212(54),186(22),171(20);HRMS(ESI)m/z:[M++Na]CalcdforC14H14O6N2NaS361.0465;Found:361.0459.6N-[(4-Acetylphenyl)(methyl)(oxo)-λ-sulfanylidene]-6-methyl-2,4-dioxo-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13fa)FollowingGP1,13fawassynthesizedfrom3f(111mg,0.500mmol,1.0equiv)and8a(372mg,2.28mmol,4.0equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasayellowsolid(26.2mg,10.0748mmol,15%).Mp:188–189°C;HNMR(600MHz,(CD3)2SO):δ=11.95(s,1H),8.30–8.03(m,4H),3.58(s,3H),2.67(s,3H),2.21(s,3H)131ppm;C{H}NMR(151MHz,(CD3)2SO):δ=197.4,169.4,164.8,160.2,147.0,141.7,140.6,129.1,127.7,113.4,42.8,27.2,17.5ppm;IR(ATR)ν=3860,3507,3353,3183,3081,3034,3010,2925,2855,2495,2323,2182,2104,2044,1982,1955,105,1832,1755,1714,1681,1641,1447,1398,1366,1323,1274,1211,1174,1107,1006,969,931,–1898,826,665cm;MS(EI)m/z:225(12),224(100),198(42),167(20),152(10),121(10);MS(CI)m/z:308(37),282(23),226(16),224(23),199(19),198(100),186(12),183(39),171(15),153+(14),128(18),121(12),85(22);HRMS(ESI)m/z:[M+Na]CalcdforC15H14O6N2NaS373.0465;Found:373.0460.66-Methyl-2,4-dioxo-N-(oxodiphenyl-λ-sulfanylidene)-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13ha)FollowingGP1,13hawassynthesizedfrom3h(121mg,0.500mmol,1.0equiv)and8a(372mg,2.28mmol,4.0equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasayellowsolid(153mg,0.413mmol,83%).Mp:204–1205°C;HNMR(600MHz,(CD3)2SO):δ=12.05(s,1H),8.12–8.06(m,4H),1317.74–7.68(m,2H),7.68–7.62(m,4H),2.24(s,3H)ppm;C{H}NMR(151MHz,(CD3)2SO):δ=169.9,166.9,160.6,147.0,138.7,134.0,130.0,127.4,113.2,17.7ppm;IR(ATR)ν=3860,3560,3400,3219,3111,2920,2856,2692,2478,2261,2217,2181,2115,2066,2006,1931,1839,1774,1700,1629,1434,1384,1315,1277,1223,1165,1112,–1997,910,836,756,723,683cm;MS(EI)m/z:245(14),244(100),218(35),151(12),125(71),+·+109(12),77(26),51(13);MS(CI)m/z:372(10)[M+2],371(49)[M+H],330(13),329(21),328(100),302(50),246(12),245(11),244(65),218(49),204(21),203(18),128(22),125(18),103+(11),101(16),85(60),83(65);HRMS(ESI)m/z:[M+Na]CalcdforC18H14O5N2NaS393.0516;Found:393.0526.

10S116N-[Cyclohexyl(methyl)(oxo)-λ-sulfanylidene]-6-methyl-2,4-dioxo-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(13ia)FollowingGP1,13iawassynthesizedfrom3i(106mg,0.569mmol,1.0equiv)and8a(424mg,2.28mmol,4.0equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasayellowsolid(52.7mg,0.168mmol,30%).Mp:1143–144°C;HNMR(600MHz,(CD3)2SO):δ=11.89(s,1H),3.55–3.46(m,1H),3.36(s,3H),2.21(s,3H),2.17–2.10(m,2H),1.92–1.78(m,2H),1.69–1.60131(m,1H),1.54–1.41(m,2H),1.39–1.22(m,2H),1.22–1.09(m,1H)ppm;C{H}NMR(151MHz,(CD3)2SO):δ=169.4,164.0,160.3,147.2,114.1,61.1,35.5,24.6,24.5,24.5,24.3,24.3,17.5ppm;IR(ATR)ν=3860,3540,3410,3174,3115,3029,2935,2860,2658,2287,2203,2078,2035,2004,1967,1932,1826,1770,1704,1620,1400,1304,1228,1172,–1+1110,974,921,893,806,752,693,661cm;MS(EI)m/z:315(10)[M+H],233(50),217(40),190(10),174(16),171(27),154(100),145(13),111(16),106(40),83(31),55(54);MS(CI)m/z:+·+343(14),316(16)[M+2],315(100)[M+H],272(11),233(44),190(21),171(46);HRMS+(ESI)m/z:[M+Na]CalcdforC13H18O5N2NaS337.0829;Found:337.0837.6(Z)-6-Methyl-N-{methyl(oxo)[4-(3-oxobut-1-en-1-yl)phenyl]-λ-sulfanylidene}-2,4-dioxo-3,4-dihydro-2H-1,3-oxazine-5-carboxamide(14)FollowingGP1,14wassynthesizedfrom3g(104mg,0.500mmol,1.0equiv)and8a(372mg,2.00mmol,4.0equiv).AfterFCC(pentane:EtOAc–1:1to1:2)theproductwasobtainedasayellowsolid(24.4mg,0.0648mmol,13%).1Mp:186–187°C;HNMR(600MHz,(CD3)2SO):δ=11.98(s,1H),8.24–8.10(m,2H),7.97–7.81(m,2H),6.85(s,1H),5.63(s,1H),3.57(s,3H),2.20(s,1313H),2.13(s,3H)ppm;C{H}NMR(151MHz,(CD3)2SO):δ=172.6,169.5,164.7,161.1,160.3,147.1,139.7,139.2,127.9,127.9,113.5,98.1,96.2,43.0,19.0,17.6ppm;IR(ATR)ν=3420,3008,2926,2804,2326,2256,2125,1920,1706,1628,1398,1338,1284,1219,1170,1112,1059,1022,901,824,756,–1663cm;MS(EI)m/z:211(10),210(100),184(23),168(18),153(17),85(11),84(28),77(37),69(72),65(12),63(30),55(13),53(23),51(22),45(28);MS(CI)m/z:268(14),169(56),167(13),+128(12),85(100);HRMS(ESI)m/z:[M+Na]CalcdforC17H16O6N2NaS399.0621;Found:399.0632.

11S124.NMRSpectra1HNMR(400MHz,CDCl3)spectrumofcompound3a131C{H}NMR(101MHz,CDCl3)spectrumofcompound3a

12S131HNMR(400MHz,CDCl3)spectrumofcompound3b131C{H}NMR(101MHz,CDCl3)spectrumofcompound3b

13S141HNMR(600MHz,CDCl3)spectrumofcompound3c131C{H}NMR(151MHz,CDCl3)spectrumofcompound3c

14S151HNMR(600MHz,CDCl3)spectrumofcompound3d131C{H}NMR(151MHz,CDCl3)spectrumofcompound3d

15S161HNMR(600MHz,CDCl3)spectrumofcompound3e131C{H}NMR(151MHz,CDCl3)spectrumofcompound3e

16S171HNMR(600MHz,CDCl3)spectrumofcompound3f131C{H}NMR(151MHz,CDCl3)spectrumofcompound3f

17S181HNMR(600MHz,CDCl3)spectrumofcompound3g131C{H}NMR(151MHz,CDCl3)spectrumofcompound3g

18S191HNMR(600MHz,CDCl3)spectrumofcompound3h131C{H}NMR(151MHz,CDCl3)spectrumofcompound3h

19S201HNMR(600MHz,CDCl3)spectrumofcompound3i131C{H}NMR(151MHz,CDCl3)spectrumofcompound3i

20S211HNMR(600MHz,CDCl3)spectrumofcompound8a131C{H}NMR(151MHz,CDCl3)spectrumofcompound8a

21S221HNMR(600MHz,CDCl3)spectrumofcompound8b131C{H}NMR(151MHz,CDCl3)spectrumofcompound8b

22S231HNMR(600MHz,CDCl3)spectrumofcompound8c131C{H}NMR(151MHz,CDCl3)spectrumofcompound8c

23S241HNMR(600MHz,CDCl3)spectrumofcompound8d131C{H}NMR(151MHz,CDCl3)spectrumofcompound8d

24S251HNMR(600MHz,CDCl3)spectrumofcompound8e131C{H}NMR(151MHz,CDCl3)spectrumofcompound8e

25S261HNMR(600MHz,CDCl3)spectrumofcompound8f131C{H}NMR(151MHz,CDCl3)spectrumofcompound8f

26S271HNMR(600MHz,(CD3)2SO)spectrumofcompound13aa131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound13aa

27S281HNMR(600MHz,(CD3)2SO)spectrumofcompound13ab131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound13ab

28S291HNMR(600MHz,(CD3)2SO)spectrumofcompound13ac131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound13ac

29S301HNMR(600MHz,(CD3)2SO)spectrumofcompound13ad131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound13ad

30S311HNMR(600MHz,(CD3)2SO)spectrumofcompound13ae131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound13ae

31S321HNMR(600MHz,(CD3)2SO)spectrumofcompound13af131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound13af

32S331HNMR(400MHz,(CD3)2SO)spectrumofcompound13ba131C{H}NMR(101MHz,(CD3)2SO)spectrumofcompound13ba

33S341HNMR(600MHz,(CD3)2SO)spectrumofcompound13ca131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound13ca

34S351HNMR(600MHz,(CD3)2SO)spectrumofcompound13da131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound13da

35S361HNMR(600MHz,(CD3)2SO)spectrumofcompound13ea131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound13ea

36S371HNMR(600MHz,(CD3)2SO)spectrumofcompound13fa131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound13fa

37S381HNMR(600MHz,(CD3)2SO)spectrumofcompound13ha131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound13ha

38S391HNMR(600MHz,(CD3)2SO)spectrumofcompound13ia131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound13ia

39S401HNMR(600MHz,(CD3)2SO)spectrumofcompound14131C{H}NMR(151MHz,(CD3)2SO)spectrumofcompound14

40S415.SingleX-raystructureof13aaSinglecrystalsof13aaweremeasuredusingadual-sourceRigakuSuperNovadiffractometerequippedwithanAtlasdetectorandanOxfordCryostreamcoolingsystemusingmirror-monochromatedMo-Kαradiation(λ=0.71073Å).Datacollectionandreductionforallcomplexes4wereperformedusingtheprogramCrysAlisProandGaussianface-indexabsorptioncorrection45a,bmethodwasapplied.ThestructurewassolvedwithDirectMethods(SHELXS)andrefinedbyfull-25cmatrixleast-squaresbasedonFusingSHELXL-2015.Non-hydrogenatomswereassignedanisotropicdisplacementparametersunlessstatedotherwise.ThehydrogenatombondedtonitrogenwaslocatedfromFourierdifferencemapsandrefinedwithanN−Hdistancerestraintofapproximately0.95Å.Otherhydrogenatomswereplacedinidealizedpositionsandincludedasriding.IsotropicdisplacementparametersforallHatomswereconstrainedtomultiplesoftheequivalentdisplacementparametersoftheirparentatomswithUiso(H)=1.2Ueq(parentatom).Onereflectionwithlargediscrepanciesbetweenthecalculatedandobservedstructurefactorshasbeenomittedfromtheleast-squaresrefinementasoutliers.TheX-raysinglecrystaldataandexperimentaldetailsaswellasCCDCnumberaregivenbelow.Crystaldatafor13aa(obtainedfromrecrystallizationfromEtOAcandpentane):CCDC-1993374,–13C13H12N2O5S,M=308.31gmol,colourlessplate,0.232×0.131×0.023mm,triclinic,spacegroupP-1(No.2),a=6.6525(6)Å,b=7.9232(7)Å,c=14.1077(13)Å,α=88.557(7)°,β=80.942(8)°,γ=3–3–167.887(8)°,V=679.84(11)Å,Z=2,Dcalc=1.506gcm,F(000)=320,µ=0.262mm,T=120(2)K,θmax=27.4°,9784totalreflections,1942withIo>2σ(Io),Rint=0.0673,2735data,195parameters,1restraints,GooF=1.039,R1=0.0561andwR2=0.1186[Io>2σ(Io)],R1=0.0868andwR2=0.1377–3(allreflections),0.451

41S426.References(1)Dannenberg,C.A.;Fritze,L.;Krauskopf,F.;Bolm,C.,AccesstoN-cyanosulfoximinesbytransitionmetal-freeiminationsofsulfoxides.Org.Biomol.Chem.2017,15,1086–1090.(2)Yamamoto,Y.;Watanabe,Y.;Ohnishi,S.,ReactionofAcylMeldrum'sAcidswithSchiffBasesGiving2,3-Disubstituted5-Acy1-3,4,5,6-tetrahydro-2H-1,3-oxazine-4,6-dionesand2,3,6-Trisubstituted2,3-Dihydro-1,3-oxazin-4-ones.Chem.Pharm.Bull.1987,35,1860–1870.(3)Khopade,T.M.;Warghude,P.K.;Mete,T.B.;Bhat,R.G.,Acyl/aroylMeldrum’sacidasanenolsurrogateforthedirectorganocatalyticsynthesisofα,β-unsaturatedketones.TetrahedronLett.2019,60,197–200.(4)RigakuOxfordDiffraction,2017,CrysAlisProsoftwaresystem,version38.46,RigakuCorporation,Oxford,UK.(5)(a)Sheldrick,G.M.,AshorthistoryofShelXL.ActaCryst.2008,A64,112–122.(b)Sheldrick,G.M.,SHELXL13.Programpackageforcrystalstructuredeterminationfromsinglecrystaldiffractiondata,UniversityofGöttingen,Germany,2013.(c)Sheldrick,G.M.,CrystalstructurerefinementwithShelXL.ActaCryst.2015,C71,3–8.