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1、底物合成路线汇报之前硝基生成叠氮的反应经过仔细查询，CA以及文献上全部都需要邻位醛基，不可取：AngewandteChemie,InternationalEdition,50(7),1702-1706;20111目标产物2合成路线一2.1步骤1Org.Lett., 2010, 12 (12),pp2884–2887Toacold(0°C)solutionofsubstituted2-aminobenzophenone(1.97g,10.0mmol,1equiv)in50mLofaceticacidand
2、50mLofwaterwasaddedsodiumnitrite(1.04g,15.0mmol,1.5equiv).Afterstirringfor1hour,sodiumazide(0.975g,15.0mmol,1.5equiv)wasaddedslowlyintothestirringmixture,andthemixturewasallowedtowarmtoambienttemperature.Afteranadditionalhourofstirring,theresultingmixtur
3、ewasneutralizedwithasaturatedaqueoussolutionofNa2CO3andextractedwith3×20mLofCH2Cl2.TheresultingorganicphasewasdriedoverNa2SO4anddecanted.Thefiltratewasconcentratedinvacuotoaffordayellowoil.PurificationbyMPLC(1:99EtOAc:hexanes)affordedtheproduct.2.2步骤2J.O
4、rg.Chem.2011,76,4715–4720Toasuspensionofmethyltriphenylphosphoniumbromide(72mmol,25.7g)inTHF(50mL)wasaddeddropwiseNaHMDS(1.0MTHF,72mL)at-78°C.Theresultingsolutionwasstirredatthistemperaturefor15min,andthenasolutionof2-nitrobenzaldehyde(60mmol,9.06g)inTHF
5、(20mL)wasadded,andtheresultingreactionmixturewasfurtherstirredatrtfor14h.ThereactionwasquenchedusingsaturatedNH4Cl(aq),andthecrudeproductwasextractedtwicewithdiethylether.ThecombinedorganiclayersweredriedoverNa2SO4andconcentratedinvacuo.Theresiduewaspuri
6、fiedbysilicagelcolumnchromatographywithn-hexane/diethylether(90/10)astheeluanttoobtaintheproduct(9.28g,95%)AngewandteChemie,InternationalEdition,52(5),1556-1559;20132.3步骤3Chem.Commun.,2013,49,2989--2991Amixtureofα-methylstyrene(3.00g,25.4mmol,1eq)andNBS(
7、5.42g,30.5mmol,1.2eq)weresuspendedinCCl4(60mL)andheatedunderrefluxforsixhours.Afterthattime,themixturewascooledandtheprecipitatedsuccinimidewasseparatedbyfiltrationandthesolventandtheexcessofα-methylstyreneremovedunderreducedpressure.Ofthe4.21goftheclear
8、yellowoilobtained,GC-MSanalysisindicatedaca.3:1ratioofproductto1-bromo-2-phenyl-1-propene.Thisproduct(S4)wasusedwithoutfurtherpurification(3.50g,70%).2.4步骤4Chem.Commun.,2013,49,2989—2991Potassiumphthalimide(2.58g,13.9mmol,
