丙酮为溶剂Pd_OAc_2催化的Heck反应研究

2323720117ChemicalResearchandApplicationVol．23No．7July20111004-1656201107-0882-06PdOAc2Heck*200240、PdOAc2Heck。PdOAc21mol%K2CO31.2equiv.100℃1equiv.、2equiv.Heck。。HeckO622.1APdOAc2-catalyzedHeckreactioninaetoneWANGZhong-huaBIRanLUWen-jun*DepartmentofChemistryShanghaiJiaoTongUniversityShanghai200240AbstractAsimpleconvenientandeffectiveHeckcouplingreactionhadbeendevelopedwhichwasaligand-freenoexternalre-ducingagentsandPd-catalyzedreaction.InthepresenceofcatalyticPdOAc2withK2CO3inacetoneanexcellentchemoselectiv-itytoarylC-Ibondshadalsobeenachievedinthesecouplingreactionsofaryliodideswithvariousterminalolefinstoaffordtrans-olefinsexclusively.KeywordsPd-catalyzedHeckreactioncouplingaryliodideHeck19711972Mi-zoroki1Heck2-。40Heck、、、、、。Heck2010。HeckDMF、MeCN、MeOHPdCl2PdOAc22345、。HeckHeck67、8-112011-04-212011-05-10208720891966-。[e-mail].7PdOAc2Heck1213HeckHeck14-16Heck17-19Heck20-22。、、Heck2324。。PdOAc2Heck、、。11.160℃。、ACROSAlfaAesar。15mL。1HNMR13CNMRVar-ianMERCURYplus400400MHzTMS。XT4A。。1.2PdOAc2Heck15mLPdOAc20.005mmol0.6mmol0.5mmol1.0mmol1mL100℃18-30h。10mL10mL×310mL3Heck1-15。E-4-12526m．p．128-129℃1HNMR400MHzCDCl3δ7.05dJ=16.4Hz1H7.10dJ=16.4Hz1H7.25-7.30m1H7.34dJ=8.2Hz2H7.40tJ=7.6Hz2H7.45dJ=8.2Hz2H7.52dJ=7.6Hz2H。E-4-2271HNMR400MHzCDCl3δ1.32tJ=7.2Hz3H4.25qJ=7.2Hz2H6.46dJ=16.0Hz1H7.36dJ=8.8Hz2H7.50dJ=8.8Hz2H7.60dJ=16.0Hz1H。E-4-3281HNMR400MHzCDCl3δ1.32tJ=7.2Hz3H4.25qJ=7.2Hz2H6.39dJ=16.0Hz1H7.34dJ=8.2Hz2H7.43dJ=8.2Hz2H7.61dJ=16.0Hz1H。E-4-429m．p．142-144°C1HNMR400MHzCDCl3δ1.33tJ=7.2Hz3H4.27qJ=7.2Hz2H6.54dJ=16.0Hz1H7.65dJ=8.8Hz2H7.69dJ=16.0Hz1H8.22dJ=8.8Hz2H。E-4-52530m．p．134-135°C1HNMR400MHzCDCl3δ7.05J=16.4Hz1H7.12dJ=16.4Hz1H7.30-7.33m1H7.37-7.41m4H7.49-7.54m4H。E-6281HNMR400MHzCDCl3δ1.34tJ=7.2Hz3H4.26qJ=7.2Hz2H6.44dJ=16.0Hz1H7.51-7.53m2H7.37-7.39m3H7.68dJ=16.0Hz1H。E-72629m．p．125-126°C1HNMR400MHzCDCl3δ7.14s2H7.29tJ=7.6Hz2H7.39tJ=7.6Hz4H7.55dJ=7.2Hz4H。E-4-8281HNMR400MHzCDCl3δ1.32tJ=7.2Hz3H3.83s3H4.24qJ=7.2Hz2H6.3038823dJ=16.0Hz1H6.90dJ=8.8Hz2H7.47dJ=8.8Hz2H7.64dJ=16.0Hz1H。E-3-9311HNMR400MHzCDCl3δ1.33tJ=7.2Hz3H3.82s3H4.26qJ=7.2Hz2H6.42dJ=16.0Hz1H6.93ddJ1=8.0HzJ2=2.8Hz1H7.04tJ=2.0Hz1H7.11dJ=7.6Hz1H7.29tJ=7.6Hz1H7.64dJ=16.0Hz1H。E-2-10311HNMR400MHzCDCl3δ1.33tJ=7.2Hz3H3.88s3H4.26qJ=7.2Hz2H6.52dJ=16.0Hz1H6.91dJ=8.2Hz1H6.95tJ=7.6Hz1H7.34tJ=7.6Hz1H7.50ddJ1=7.6HzJ2=1.6Hz1H7.99dJ=16.4Hz1H。E-4-112932m．p．138-139°C1HNMR400MHzCDCl3δ3.84s3H6.92dJ=8.2Hz2H6.99dJ=16.4Hz1H7.09dJ=16.0Hz1H7.25m1H7.36tJ=8.0Hz2H7.47dJ=8.2Hz2H7.51dJ=8.0Hz2H。E-3-12331HNMR400MHzCDCl3δ3.86s3H6.83ddJ1=8.0HzJ2=2.4Hz1H7.06tJ=2.0Hz1H7.10dJ=1.6Hz2H7.12dJ=7.6Hz1H7.26-7.30m2H7.35-7.38m2H7.52dJ=7.2Hz2H。E-2-13291HNMR400MHzCDCl3δ3.90s3H6.91dJ=8.0Hz1H6.98dJ=7.6Hz1H7.12dJ=16.4Hz1H7.23-7.27m2H7.36tJ=7.6Hz2H7.50dJ=16.4Hz1H7.55dJ=7.2Hz2H7.61ddJ1=8.0HzJ2=1.6Hz1H。E-2--4-14341HNMR400MHzCDCl3δ1.16-1.34m6H1.76-1.83m4H2.07-2.13m1H6.03ddJ1=16.0HzJ2=6.8Hz1H6.28dJ=16.0Hz1H6.83dJ=8.8Hz2H7.27dJ=8.8Hz2H。E-1-15351HNMR400MHzCDCl3δ1.38tJ=7.2Hz3H4.32qJ=7.2Hz2H6.53dJ=15.6Hz1H7.48tJ=8.0Hz1H7.51-7.55m1H7.55dJ=7.2Hz1H7.56-7.60m1H7.88dJ=8.0Hz2H8.20dJ=8.4Hz1H8.53dJ=16.0Hz1H。22.11K2CO3CF3CO2AgKOAc、Na2CO31Entries1-5K2CO3。PdOAc21Entries6-10PdOAc2。2.21mol%1Entry11。TLC0.1mol%80%1Entry170.01mol%90h39%1Entry18。1mol%。60℃80℃1Entries1213100℃120℃1Entry16。1/2mmol/mmol1Entries1415。4887PdOAc2Heck1HeckaTable1Optimizationofthecouplingof1-chloro-4-iodobenzenewithstyreneaEntryCatalystmol%AdditiveTimehT℃Yield%b11%PdOAc2—20100trace25%PdOAc2KOAc201004235%PdOAc2Na2CO320100524c5%PdOAc2CF3CO2Ag201008955%PdOAc2K2CO3171008065%PdTFA2K2CO3171006275%PdPPh32Cl2K2CO3171006285%PdPPh34K2CO3181003195%Pd/CK2CO3171005010d5%PdCl2K2CO31710014111%PdOAc2K2CO32010086125%PdOAc2K2CO3186053135%PdOAc2K2CO320807114e5%PdOAc2K2CO3201006915e1%PdOAc2K2CO31712078161%PdOAc2K2CO31712089170.1%PdOAc2K2CO35010081180.01%PdOAc2K2CO3901003919f1%PdOAc2K2CO31810042aConditions1-chloro-4-iodobenzene0.5mmolstyrene1.0mmoladditive0.6mmolacetone1.0mLbyieldbasedon1-chloro-4-iodobenzenecCF3CO2Ag1.0mmoldyieldbasedonaryli-odideanddetectedby1HNMRCH2Br2astheinternalstandardesty-rene0.6mmolfbutanone1.0mLinsteadofacetone.2.31mol%PdOAc21.2equiv.K2CO3100℃。1Heck100%。2-。2。1HeckaFig．1Pd-CatalyzedcouplingofaryliodideswithterminalplefinsinacetoneaaTherightsubstitutedarylgroupsofinternalalkenesarefromaryliodides.2.4C-I、C-Br。16。12122120℃1668%。2222、、NN－DMA、1645%。E-4--E-58823m．p．144-146°C1HNMR400MHzCDCl3δ1.35tJ=7.2Hz3H4.28qJ=7.2Hz2H6.44dJ=16.0Hz1H7.09dJ=16.4Hz1H7.17dJ=16.4Hz1H7.28tJ=7.2Hz1H7.36tJ=7.2Hz2H7.51-7.52m6H7.67dJ=16.0Hz1H13CNMR100MHzCDCl3δ14.360.4117.7126.6126.8127.7127.9128.4128.7130.0133.6136.9139.2144.0167.0MSm/z280.1279.1MH+HRMSm/zM+H+CalcdforC19H19O2279.1380found279.1391。12216Fig．2Preparationoftranstrans-3-4-styryl-phenyl-acrylicacidethylester3Heck。PdOAc2K2CO3、、Heck。、Heck。1MizorokiTMoriKOzakiA．ArylationofolefinwitharyliodidecatalyzedbypalladiumJ．Bull．Chem．Soc．Jpn．197144581-581．2HeckRFNolleyJP．Palladium-catalyzedvinylichydro-gensubstitutionreactionswitharylbenzylandstyrylhal-idesJ．J．Org．Chem．197237142320-2322．3DeVriesAHMMuldersJMCAMommersJHMetal.Homeopathicligand-freepallad