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CatalyticAsymmetricHenryReactionCatalyticAsymmetricHenryReaContents1、Introduction2、Metalbasedchiralcatalyst3、OrganocatalyticHenryreaction4、ConclusionandoutlookContents1、IntroductionHenryReaction－C-Cbodnformingreaction1、IntroductionHenryReaction－C-Cbodnform2.1Rareearth-BINOLcomplexesRnitroalkaneyieldSyn:antieeofsynPhCH2CH3CH2NO270%89:1196%PHCH2CH2CH3(CH2)2NO285%93:798%PHCH2CH2OH(CH2)2NO297%92:898%CH3(CH2)4OH(CH2)2NO295%92:898%Shibasaki,M.etal,J.Am.Chem.Soc.1992,114:4418;

J.Am.Chem.Soc.1993,115:10372

TetrahedronLett.1993,34:851;.

TetragedronLett.1993,34:2657;

Tetrahedron1994,50:12313;

TetrahedronLett.1994,35:6123;

J.Org.Chem.1995,60:7388;

Apll.Organomet.Chem.1995,9:421;

TetrahedronLett.1996,37:9081;

Heterocycles1997,46:157;

TetrahedronLett.2004,45:3689.2、Metalbasedchiralcatalysts2.1Rareearth-BINOLcomplexes2.1Rareearth-BINOLcomplexes2.1Rareearth-BINOLcomplexes2.2Zn-ligandcatalysts2.2.1DinuclearZncatalystsBarryM.Trost,Angew.Chem.Int.Ed.2002,41:861;Org.Lett.2002,4:2621.2.2Zn-ligandcatalystsZn-Ligandcatalysts2.2.1DinuclearZncatalysts2.2Zn-LigandcatalystsZn-ligandcatalysts2.2.2DualLewisacid/aminechiralaminoalcoholligandClaudioPalomo,Angew.Chem.Int.Ed.2005,44:38812.2Zn-ligandcatalysts2.2.2D2.2Zn-Ligandcatalysts2.2.3Diethylzinctriggreedreactions[1]Guo-qiangLin,Tetrahedron:Asymmetric2004,15:771;[2]A.E.Martell,Org.Biomol.CHem.2003,1:2801.2.2Zn-Ligandcatalysts2.2.3D2.3Copper-Ligandcatalysts2.3.1Cu-Bis(oxazoline)(BOX)catalystsK.A.Jorgensen,Chem.Commun.2001:2222;

J.Org.Chem.2002,667:4875;

Org.Biomol.Chem.2003,1:153.2.3Copper-Ligandcatalysts2.32.3Copper-LigandcatalystsentryRYield(%)Ee(%)1Ph769422-MeOC6H4919331-naphthyl66874PhCH2CH281905t-Bu83946n-Bu87937cyclohexyl95932.3.1Cu-Bis(oxazoline)(BOX)catalystsDavidA.Evans,J.Am.Chem.Soc.2003,125:12692.2.3Copper-Ligandcatalystsent2.3Copper-Ligandcatalysts2.3.2CopperSchiff-basecomplexsMing-mingZhouetal,Tetrahedron:Asymmetric2006,17:725.2.3Copper-LigandcatalystsDiaminecatalystsentryRYield(%)Ee(%)1C6H5>957924-NO2-C6H4908632-NO2-C6H4808944-MeO-C6H4>958052-MeO-C6H4>959764-Cl-C6H4808172-Cl-C6H4609681-naphthyl82739cyclohexyl858510n-butyl787811Isobutyl809012n-propyll8481H.MAheswaran,Chem.Commun.2006:40DiaminecatalystsentryRY2.3Copper-Ligandcatalysts2.3.3DiaminecatalystsTakayoshiArai,Org.Lett.2007,9:35952.3Copper-Ligandcatalysts2.32.3Copper-Ligandcatalysts2.3.3DiaminecatalystsEntryAldehydeXmol(%)Yield(%)ee{(%)112>99902116692323>9980435829054566866558586765>99868729990TakayoshiArai,Angew.Chem.Int.Ed.2006,45:5978.2.3Copper-Ligandcatalysts2.32.3Copper-Ligandcatalysts2.3.3DiaminecatalystsentryMetalsalt(10mol%)baseT(℃)YieldEe(%)1Cu(OAc)2-2H2O-rt94rac2Ni(OAc)2-4H2O-rt94rac3Zn(OAc)2-2H2O-rt77-104Pd(OAc)2-2H2O-rt40375Cu(OAc)2-H2O-rt93616Cu(OAc)2-H2OCy2NH-6584807Cu(OAc)2-H2OEt3N-6556838Cu(OAc)2-H2ODIPEA-659085J.R.Pedroetal.Tetrahedron:Asymmetry2006,17:2046;Tetrahedron:Asymmetry2007,18:1603.2.3Copper-Ligandcatalysts2.32.3Copper-Ligandcatalysts2.3.3DiaminecatalystsMarcoBandinietal,Chem.Commun.2007:616.2.3Copper-Ligandcatalysts2.32.3Copper-Ligandcatalysts2.3.4OthercomplexXiaomingFeng,Chem.Eur.J.2007,13:829.2.3Copper-Ligandcatalysts2.32.3Copper-Ligandcatalysts2.3.4OthercomplexXiaomingFeng,jo701898r2.3Copper-Ligandcatalysts2.32.3Copper-Ligandcatalysts2.3.4OthercomplexJ.J.Jiang,M.Shi,Tetrahedron:Asymmetry2007,18:1376.2.3Copper-Ligandcatalysts2.3JiaxiXuetal,TetrahedronLett.2004,15:3433;

Chem.Eur.J.2007,13:1863;JinsongYongetal,J.Org.Chem.2005,70:3712.JiaxiXuetal,TetrahedronLe2.5KetoaminocobaltcomplexsentryRinaldehydeYield(%)Ee(%)1Phquant812p-ClPhquant853o-ClPhquant914p-CF3Ph93905o-OMePhquant9062-naphthylquant847PhCH=CH-72798c-Hex9173TohruYamada,Chem.Lett.2004,33:614.2.5Ketoaminocobaltcomplexse3、OrganocatalyticHenryreaction3、OrganocatalyticHenryreacti3.1Guanidinederivedorganocatalysis3.1.1EnantiopureguanidinecatalysisCarmenNajera,Tetrahedron:Asymmetry1993,5:1393.3.1Guanidinederivedorganoca3.1Guanidinederivedorganocatalysis3.1.1EnantiopureguanidinecatalysisDaweiMaetal,TetrahedronLett.2002,43:9401.3.1Guanidinederivedorganoca3.1Guanidinederivedorganocatalysis3.1.2GuanidinebasedbifunctionalcatalysisKazuoNagasawaetal,Adv.Synth.Catal.2005,347:1643.3.1Guanidinederivedorganoca3.2CinchonaalkaloidderivedorganocatalysisHiemstraH.,Synlett2005:2718;

Angew.Chem.Int.Ed.2006,45:929.3.2Cinchonaalkaloidderived3.2CinchonaalkaloidderivedorganocatalysisLiDeng,J.Am.Chem.Soc.2006,128,732.3.2Cinchonaalkaloidderived3.2CinchonaalkaloidderivedorganocatalysisCong-GuiZhao,Org.Lett.2007,9:59433.2Cinchonaalkaloidderived3.3SilylnitronatesasactivatednitroalkanesKeijiMaruoka,J.Am.Chem.Soc.2003,125:2054.3.3Silylnitronatesasactiva3.4ChiralTetraamino-phosphoniumSaltTakashiOoi,J.AM.CHEM.SOC.2007,129:12392.3.4ChiralTetraamino-phospho3.5chiralSchiff-baseligandsNadirDemireletal.,Tetrahedron:Asymmetry2007,18:1129.3.5chiralSchiff-baseligandsCatalyticAsymmetricHenryReactionCatalyticAsymmetricHenryReaContents1、Introduction2、Metalbasedchiralcatalyst3、OrganocatalyticHenryreaction4、ConclusionandoutlookContents1、IntroductionHenryReaction－C-Cbodnformingreaction1、IntroductionHenryReaction－C-Cbodnform2.1Rareearth-BINOLcomplexesRnitroalkaneyieldSyn:antieeofsynPhCH2CH3CH2NO270%89:1196%PHCH2CH2CH3(CH2)2NO285%93:798%PHCH2CH2OH(CH2)2NO297%92:898%CH3(CH2)4OH(CH2)2NO295%92:898%Shibasaki,M.etal,J.Am.Chem.Soc.1992,114:4418;

J.Am.Chem.Soc.1993,115:10372

TetrahedronLett.1993,34:851;.

TetragedronLett.1993,34:2657;

Tetrahedron1994,50:12313;

TetrahedronLett.1994,35:6123;

J.Org.Chem.1995,60:7388;

Apll.Organomet.Chem.1995,9:421;

TetrahedronLett.1996,37:9081;

Heterocycles1997,46:157;

TetrahedronLett.2004,45:3689.2、Metalbasedchiralcatalysts2.1Rareearth-BINOLcomplexes2.1Rareearth-BINOLcomplexes2.1Rareearth-BINOLcomplexes2.2Zn-ligandcatalysts2.2.1DinuclearZncatalystsBarryM.Trost,Angew.Chem.Int.Ed.2002,41:861;Org.Lett.2002,4:2621.2.2Zn-ligandcatalystsZn-Ligandcatalysts2.2.1DinuclearZncatalysts2.2Zn-LigandcatalystsZn-ligandcatalysts2.2.2DualLewisacid/aminechiralaminoalcoholligandClaudioPalomo,Angew.Chem.Int.Ed.2005,44:38812.2Zn-ligandcatalysts2.2.2D2.2Zn-Ligandcatalysts2.2.3Diethylzinctriggreedreactions[1]Guo-qiangLin,Tetrahedron:Asymmetric2004,15:771;[2]A.E.Martell,Org.Biomol.CHem.2003,1:2801.2.2Zn-Ligandcatalysts2.2.3D2.3Copper-Ligandcatalysts2.3.1Cu-Bis(oxazoline)(BOX)catalystsK.A.Jorgensen,Chem.Commun.2001:2222;

J.Org.Chem.2002,667:4875;

Org.Biomol.Chem.2003,1:153.2.3Copper-Ligandcatalysts2.32.3Copper-LigandcatalystsentryRYield(%)Ee(%)1Ph769422-MeOC6H4919331-naphthyl66874PhCH2CH281905t-Bu83946n-Bu87937cyclohexyl95932.3.1Cu-Bis(oxazoline)(BOX)catalystsDavidA.Evans,J.Am.Chem.Soc.2003,125:12692.2.3Copper-Ligandcatalystsent2.3Copper-Ligandcatalysts2.3.2CopperSchiff-basecomplexsMing-mingZhouetal,Tetrahedron:Asymmetric2006,17:725.2.3Copper-LigandcatalystsDiaminecatalystsentryRYield(%)Ee(%)1C6H5>957924-NO2-C6H4908632-NO2-C6H4808944-MeO-C6H4>958052-MeO-C6H4>959764-Cl-C6H4808172-Cl-C6H4609681-naphthyl82739cyclohexyl858510n-butyl787811Isobutyl809012n-propyll8481H.MAheswaran,Chem.Commun.2006:40DiaminecatalystsentryRY2.3Copper-Ligandcatalysts2.3.3DiaminecatalystsTakayoshiArai,Org.Lett.2007,9:35952.3Copper-Ligandcatalysts2.32.3Copper-Ligandcatalysts2.3.3DiaminecatalystsEntryAldehydeXmol(%)Yield(%)ee{(%)112>99902116692323>9980435829054566866558586765>99868729990TakayoshiArai,Angew.Chem.Int.Ed.2006,45:5978.2.3Copper-Ligandcatalysts2.32.3Copper-Ligandcatalysts2.3.3DiaminecatalystsentryMetalsalt(10mol%)baseT(℃)YieldEe(%)1Cu(OAc)2-2H2O-rt94rac2Ni(OAc)2-4H2O-rt94rac3Zn(OAc)2-2H2O-rt77-104Pd(OAc)2-2H2O-rt40375Cu(OAc)2-H2O-rt93616Cu(OAc)2-H2OCy2NH-6584807Cu(OAc)2-H2OEt3N-6556838Cu(OAc)2-H2ODIPEA-659085J.R.Pedroetal.Tetrahedron:Asymmetry2006,17:2046;Tetrahedron:Asymmetry2007,18:1603.2.3Copper-Ligandcatalysts2.32.3Copper-Ligandcatalysts2.3.3DiaminecatalystsMarcoBandinietal,Chem.Commun.2007:616.2.3Copper-Ligandcatalysts2.32.3Copper-Ligandcatalysts2.3.4OthercomplexXiaomingFeng,Chem.Eur.J.2007,13:829.2.3Copper-Ligandcatalysts2.32.3Copper-Ligandcatalysts2.3.4OthercomplexXiaomingFeng,jo701898r2.3Copper-Ligandcatalysts2.32.3Copper-Ligandcatalysts2.3.4OthercomplexJ.J.Jiang,M.Shi,Tetrahedron:Asymmetry2007,18:1376.2.3Copper-Ligandcatalysts2.3JiaxiXuetal,TetrahedronLett.2004,15:3433;

Chem.Eur.J.2007,13:1863;JinsongYongetal,J.Org.Chem.2005,70:3712.JiaxiXuetal,TetrahedronLe2.5KetoaminocobaltcomplexsentryRinaldehydeYield(%)Ee(%)1Phquant812p-ClPhquant853o-ClPhquant914p-CF3Ph93905o-OMePhquant9062-naphthylquant847PhCH=CH-72798c-Hex9173TohruYamada,Chem.Lett.2004,33:614.2.5Ketoaminocobaltcomplexse3、OrganocatalyticHenryreaction3、OrganocatalyticHenryreacti3.1Gu

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