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Catalytic Asymmetric Henry ReactionCatalytic Asymmetric Henry ReaContents1、Introduction2、Metal based chiral catalyst3、Organocatalytic Henry reaction4、Conclusion and outlookContents1、IntroductionHenry Reaction C-C bodn forming reaction1、IntroductionHenry Reaction C-C bodn form2.1 Rare earth-BINOL complexesRnitroalkaneyieldSyn:antiee of synPhCH2CH3CH2NO270%89:1196%PHCH2CH2CH3(CH2)2NO285%93:798%PHCH2CH2OH(CH2)2NO297%92:898%CH3(CH2)4OH(CH2)2NO295%92:898%Shibasaki,M.et al,J.Am.Chem.Soc.1992,114:4418;J.Am.Chem.Soc.1993,115:10372 Tetrahedron Lett.1993,34:851;.Tetragedron Lett.1993,34:2657;Tetrahedron 1994,50:12313;Tetrahedron Lett.1994,35:6123;J.Org.Chem.1995,60:7388;Apll.Organomet.Chem.1995,9:421;Tetrahedron Lett.1996,37:9081;Heterocycles 1997,46:157;Tetrahedron Lett.2004,45:3689.2、Metal based chiral catalysts2.1 Rare earth-BINOL complexes2.1 Rare earth-BINOL complexes2.1 Rare earth-BINOL complexes2.2 Zn-ligand catalysts2.2.1 Dinuclear Zn catalystsBarry M.Trost,Angew.Chem.Int.Ed.2002,41:861;Org.Lett.2002,4:2621.2.2 Zn-ligand catalysts2.2.1 2.2 Zn-Ligand catalysts2.2.1 Dinuclear Zn catalysts2.2 Zn-Ligand catalysts2.2.1 2.2 Zn-ligand catalysts2.2.2 Dual Lewis acid/amine chiral amino alcohol ligandClaudio Palomo,Angew.Chem.Int.Ed.2005,44:38812.2 Zn-ligand catalysts2.2.2 D2.2 Zn-Ligand catalysts2.2.3 Diethyl zinc triggreed reactions1 Guo-qiang Lin,Tetrahedron:Asymmetric 2004,15:771;2 A.E.Martell,Org.Biomol.CHem.2003,1:2801.2.2 Zn-Ligand catalysts2.2.3 D2.3 Copper-Ligand catalysts2.3.1 Cu-Bis(oxazoline)(BOX)catalystsK.A.Jorgensen,Chem.Commun.2001:2222;J.Org.Chem.2002,667:4875;Org.Biomol.Chem.2003,1:153.2.3 Copper-Ligand catalysts2.32.3 Copper-Ligand catalystsentryRYield(%)Ee(%)1Ph769422-MeOC6H4919331-naphthyl66874PhCH2CH281905t-Bu83946n-Bu87937cyclohexyl95932.3.1 Cu-Bis(oxazoline)(BOX)catalystsDavid A.Evans,J.Am.Chem.Soc.2003,125:12692.2.3 Copper-Ligand catalystsent2.3 Copper-Ligand catalysts2.3.2 Copper Schiff-base complexsMing-ming Zhou et al,Tetrahedron:Asymmetric 2006,17:725.2.3 Copper-Ligand catalysts2.32.3.3 Diamine catalystsentryRYield(%)Ee(%)1C6H5957924-NO2-C6H4908632-NO2-C6H4808944-MeO-C6H4958052-MeO-C6H4959764-Cl-C6H4808172-Cl-C6H4609681-naphthyl82739cyclohexyl858510n-butyl787811Isobutyl809012n-propyll8481H.MAheswaran,Chem.Commun.2006:4066.2.3.3 Diamine catalystsentryRY2.3 Copper-Ligand catalysts2.3.3 Diamine catalystsTakayoshi Arai,Org.Lett.2007,9:35952.3 Copper-Ligand catalysts2.32.3 Copper-Ligand catalysts2.3.3 Diamine catalystsEntryAldehydeXmol(%)Yield(%)ee(%)11299902116692323998043582905456686655858676599868729990Takayoshi Arai,Angew.Chem.Int.Ed.2006,45:5978.2.3 Copper-Ligand catalysts2.32.3 Copper-Ligand catalysts2.3.3 Diamine catalystsentryMetal salt(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.Pedro et al.Tetrahedron:Asymmetry 2006,17:2046;Tetrahedron:Asymmetry 2007,18:1603.2.3 Copper-Ligand catalysts2.32.3 Copper-Ligand catalysts2.3.3 Diamine catalystsMarco Bandini et al,Chem.Commun.2007:616.2.3 Copper-Ligand catalysts2.32.3 Copper-Ligand catalysts2.3.4 Other complexXiao ming Feng,Chem.Eur.J.2007,13:829.2.3 Copper-Ligand catalysts2.32.3 Copper-Ligand catalysts2.3.4 Other complexXiaoming Feng,jo701898r2.3 Copper-Ligand catalysts2.32.3 Copper-Ligand catalysts2.3.4 Other complexJ.J.Jiang,M.Shi,Tetrahedron:Asymmetry 2007,18:1376.2.3 Copper-Ligand catalysts2.3Jiaxi Xu et al,Tetrahedron Lett.2004,15:3433;Chem.Eur.J.2007,13:1863;Jinsong Yong et al,J.Org.Chem.2005,70:3712.Jiaxi Xu et al,Tetrahedron Le2.5 Ketoamino cobalt complexsentryR in aldehydeYield(%)Ee(%)1Phquant812p-ClPhquant853o-ClPhquant914p-CF3Ph93905o-OMePhquant9062-naphthylquant847PhCH=CH-72798c-Hex9173Tohru Yamada,Chem.Lett.2004,33:614.2.5 Ketoamino cobalt complexse3、Organocatalytic Henry reaction3、Organocatalytic Henry reacti3.1 Guanidine derived organocatalysis3.1.1 Enantiopure guanidine catalysisCarmen Najera,Tetrahedron:Asymmetry 1993,5:1393.3.1 Guanidine derived organoca3.1 Guanidine derived organocatalysis3.1.1 Enantiopure guanidine catalysisDawei Ma et al,Tetrahedron Lett.2002,43:9401.3.1 Guanidine derived organoca3.1 Guanidine derived organocatalysis3.1.2 Guanidine based bifunctional catalysisKazuo Nagasawa et al,Adv.Synth.Catal.2005,347:1643.3.1 Guanidine derived organoca3.2 Cinchona alkaloid derived organocatalysisHiemstra H.,Synlett 2005:2718;Angew.Chem.Int.Ed.2006,45:929.3.2 Cinchona alkaloid derived 3.2 Cinchona alkaloid derived organocatalysisLi Deng,J.Am.Chem.Soc.2006,128,732.3.2 Cinchona alkaloid derived 3.2 Cinchona alkaloid derived organocatalysisCong-Gui Zhao,Org.Lett.2007,9:59433.2 Cinchona alkaloid derived 3.3 Silyl nitronates as activated nitroalkanesKeiji Maruoka,J.Am.Chem.Soc.2003,125:2054.3.3 Silyl nitronates as activa3.4 Chiral Tetraamino-phosphonium SaltTakashi Ooi,J.AM.CHEM.SOC.2007,129:12392.3.4 Chiral Tetraamino-phospho3.5 chiral Schiff-base ligandsNadir Demirel et al.,Tetrahedron:Asymmetry 2007,18:1129.3.5 chiral Schiff-base ligands
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