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Conjugated Addition of Amines to Electron Deficient Alkenes: A Green Approach

Anindita Mukherjee, Rana Chatterjee, Aramita De, Satyajit Samanta, Sachinta Mahato, Nirnita Chakraborty Ghosal, G. V. Zyryanov, Adinath Majee


A very simple approach has been developed for conjugate addition of a variety of aliphatic and aromatic amines to electron deficient alkenes in presence tea extract at room temperature. General applicability, operational simplicity, aqueous media, mild reaction conditions, environment friendly, high yields and applications of inexpensive and easily available catalyst are the advantages of the present procedure.


Michael addition; amines; α, β-ethylenic compounds; tea extract

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Permutter P. Conjugated Addition Reactions in Organic Synthesis. Oxford: Pergamon Press; 1992. 373 p.

Bartoli G, Cimarelli C, Marcantoni E, Palmieri G, Petrini M. Chemo- and diastereoselective reduction of β-enamino esters: A convenient synthesis of both cis- and trans-γ-amino alcohols and β-amino esters. J Org Chem. 1994;59(18):5328-35. doi:10.1021/jo00097a039.

Elango S, Yan TH. A short synthesis of (+)-narciclasine via a strategy derived from stereocontrolled epoxide formation and SnCl4-catalyzed arene-epoxide coupling.J Org Chem. 2002;67(20):6954-9. doi:10.1021/jo020155k.

Elango S, Yan TH. A short synthesis of (+)-lycoricidine. Tetrahedron. 2002;58(36):7335-8. doi:10.1016/S0040-4020(02)00736-6.

Banik BK, Becker FF, Banik I. Synthesis of anticancer β-lactams: Mechanism of action. Bioorg Med Chem. 2004;12(10):2523-8. doi:10.1016/j.bmc.2004.03.033.

Graul A, Castaner J. Atorvastatin calcium. Hypolipidemic HMG-CoA reductase inhibitor. Drugs Future. 1997;22(9):956. PMID:9399600.

Ishitani H, Ueno M, Kobayashi S. Enantioselective mannich-type reactions using a novel chiral zirconium catalyst for the synthesis of optically active β-amino acid derivatives. J Am Chem Soc. 2000;122(34):8180-6. doi:10.1021/ja001642p.

Jenner G. Catalytic high pressure synthesis of hindered β-aminoesters. Tetrahedron Lett. 1995;36(2):233-6. doi:10.1016/0040-4039(94)02215-W.

D’Angelo J, Maddaluno J. Enantioselective Synthesis of B-Amino Esters through High-Pressure-Induced Addition of Amines to A, B-Ethylenic Esters. J Am Chem Soc. 1986;108(25):8112-4. doi:10.1021/ja00285a051.

Matsubara S, Yoshiyoka M, Utimoto K. Lanthanoid Triflate Catalyzed Conjugate Addition of Amines to α, β-Unsaturated Esters. A Facile Route to Optically Active β-Lactam. Chem Lett. 1994;23(5):827-30. doi:10.1246/cl.1994.827.

Bartoli G, Bartolacci M, Giuliani A, Marcantoni E, Massimo M, Torregiani E. Improved heteroatom nucleophilic addition to electron-poor alkenes promoted by CeCl3·7H2O/NaI system supported on alumina in solvent-free conditions. J Org Chem. 2005;70(1):169-74. doi:10.1021/jo048329g.

Loh TP, Wei LL. Indium trichloride-catalyzed conjugate addition of amines to α,β-ethylenic compounds in water. Synlett. 1998;9:975-6. doi:10.1016/j.tetlet.2005.03.112.

Wabnitz TC, Spencer JB. Convenient synthesis of Cbz-protected β-amino ketones by a copper-catalysed conjugate addition reaction. Tetrahedron Lett. 2002;43(21):3891-4. doi:10.1016/S0040-4039(02)00654-8.

Xu LW, Li JW, Xia CG, Zhou SL, Hu XX. Efficient Copper-Catalyzed Chemo Selective Conjugate Addition of Aliphatic Amines to α,β-Unsaturated Compounds in Water. Synlett. 2003;25:2425-7. doi:10.1055/s-2003-42125.

Duan Z, Xuan X, Li T, Yang C, Wu Y. Cerium(IV) ammonium nitrate (CAN) catalyzed aza-Michael addition of amines to α,β-unsaturated electrophiles. Tetrahedron Lett. 2006;47(31):5433-6. doi:10.1016/j.tetlet.2006.05.182.

Yang L, Xu LW, Xia CG. Highly efficient KF/Al2O3-catalyzed versatile hetero-Michael addition of nitrogen, oxygen, and sulfur nucleophiles to α,β-ethylenic compounds. Tetrahedron Lett. 2005;46(19):3279-82. doi:10.1016/j.tetlet.2005.03.112.

Shaikh NS, Deshpande VH, Bedekar AV. Clay catalyzed chemoselective Michael type addition of aliphatic amines to α,β-ethylenic compounds. Tetrahedron. 2001;57(43):9045-8. doi:10.1016/S0040-4020(01)00911-5.

Azizi N, Saidi MR. LiClO4 accelerated Michael addition of amines to α,β-unsaturated olefins under solvent-free conditions. Tetrahedron. 2004;60(2):383-7. doi:10.1016/j.tet.2003.11.012.

Varala R, Alam MM, Adapa SR. Chemoselective Michael type addition of aliphatic amines to α,β-ethylenic compounds using bismuth triflate catalyst. Synlett.2003;5:720-2. doi:10.1055/s-2003-38345.

Srivastava N, Banik BK. Bismuth nitrate-catalyzed versatile Michael reactions. J Org Chem. 2003;68(6):2109-14. doi:10.1021/jo026550s.

Reboule I, Gil R, Collin J. Aza-Michael reactions catalyzed by samarium diiodide.Tetrahedron Lett. 2005;46(45):7761-4. doi:10.1016/j.tetlet.2005.09.039.

Kantam ML, Neeraja V, Kavita B, Neelima B, Chaudhuri MK, Hussain S. Cu(acac)2 immobilized in ionic liquids: A recoverable and reusable catalytic system for aza-Michael reactions. Adv Synth Catal. 2005;347(6):763-6. doi:10.1002/adsc.200404361.

Xu, LW, Li JW, Zhou SL, Xia CG. A green, ionic liquid and quaternary ammonium salt-catalyzed aza-Michael reaction of α,β-ethylenic compounds with amines in water. New J Chem. 2004;28(2):183-4. doi:10.1039/b312047c.

Karodia N, Liu X, Ludley P, Pletsas D, Stevenson G. The ionic liquid ethyltri-n-butylphosphonium tosylate as solvent for the acid-catalysed hetero-Michael reaction. Tetrahedron. 2006;62(48):11039-43. doi:10.1016/j.tet.2006.09.052.

Chaudhuri MK, Hussain S, Kantam ML, Neelima B. Boric acid: A novel and safe catalyst for aza-Michael reactions in water. Tetrahedron Lett. 2005;46(48):8329-31. doi:10.1016/j.tetlet.2005.09.167.

Hussain S, Bharadwaj SK, Chaudhuri MK, Kalita H. Borax as an efficient metal-free catalyst for hetero-Michael reactions in an aqueous medium. Eur J Org Chem. 2007;2:374-8. doi:10.1002/ejoc.200600691.

Hashemi MM, Eftekhari-Sis B, Abdollahifar A, Khalili B. ZrOCl2·8H2O on montmorillonite K10 accelerated conjugate addition of amines to α,β-unsaturated alkenes under solvent-free conditions. Tetrahedron. 2006;62(4):672-7. doi:10.1016/j.tet.2005.10.006.

Surendra K, Krishnaveni NS, Sridhar R, Rao KR. β-Cyclodextrin promoted aza-Michael addition of amines to conjugated alkenes in water.Tetrahedron Lett.2006;47(13):2125-7. doi:10.1016/j.tetlet.2006.01.124.

Khan AT, Parvin T, Gazi S, Choudhury LH. Bromodimethylsulfonium bromide mediated Michael addition of amines to electron deficient alkenes. Tetrahedron Lett. 2007;48(22):3805-8. doi:10.1016/j.tetlet.2007.03.163.

Fetterly BM, Jana NK, Verkade JG. [HP(HNCH2CH2)3N]NO3: An efficient homogeneous and solid-supported promoter for aza and thia-Michael reactions and for Strecker reactions. Tetrahedron. 2006;62(2-3):440-56. doi:10.1016/j.tet.2005.09.117.

Roy A, Kundu D, Kundu SK, Majee A, Hajra A. Manganese (II) chloride-catalyzed conjugated addition of amines to electron deficient alkenes in methanol-water medium. The Open Catalysis Journal.2010;3(1):34-9. doi:10.2174/1876214X01003010034.

Ranu BC, Dey SS, Hajra A. Solvent-free, catalyst-free Michael-type addition of amines toelectron-deficient alkenes. ARKIVOC. 2002;7:76-81. doi:10.3998/ark.5550190.0003.709.

Ranu BC, Banerjee S. Significant rate acceleration of the aza-Michael reaction in water. Tetrahedron Lett. 2007;48(1):141-3. doi:10.1016/j.tetlet.2006.10.142.

Kobayashi S, Manabe K. Development of novel Lewis acid catalysts for selective organic reactions in aqueous media. Acc Chem Res. 2002;35(2):209-17. doi:10.1021/ar000145a.

Kobayashi S, Sugiura M, Kitagawa H, Lam W WL. Rare-earth metal triflates in organic synthesis. Chem Rev. 2002;102(6):2227-302. doi:10.1021/cr010289i.

Mallikarjuna NN, Varma RS. Green synthesis of silver and palladium nanoparticles at room temperature using coffee and tea extract. Green Chem. 2008;10(8):859-62. doi:10.1039/b804703k.

Vuong QV, Golding JB, Stathopoulos CE, Roach PD. Effects of aqueous brewing solution pH on the extraction of the major green tea constituents. Food Res Int.2013;53(2):713-9. doi:10.1016/j.foodres.2012.09.017.

Ghosal NC, Santra S, Das S, Hajra A, Zyryanov GV, Majee A. Organocatalysis by an aprotic imidazolium zwitterion: Regioselective ring-opening of aziridines and applicable to gram scale synthesis. Green Chem. 2016;18(2):565-74. doi:10.1039/c5gc01323b.

Santra S, Kopchuk DS, Kovalev IS, Zyryanov GV, Majee A, Charushin VN, Chupakhin ON. Solvent-free synthesis of pillar[6]arenes. Green Chem. 2016;18(2):423-6. doi:10.1039/c5gc01505g.

Mahato S, Santra S, Chatterjee R, Zyryanov GV, Hajra A, Majee A. Brønsted acidic ionic liquid-catalyzed tandem reaction: an efficient approach towards regioselective synthesis of pyrano[3,2-c]coumarins under solvent-free conditions bearing lower E-factors. Green Chem. Forthcoming 2017. doi:10.1039/c7gc01158j.

Santra S, Rahman M, Roy A, Majee A, Hajra A. Nano-indium oxide: An efficient catalyst for one-pot synthesis of 2,3-dihydroquinazolin-4(1H)-ones with a greener prospect. Catal Commun. 2014;49:52-7. doi:10.1016/j.catcom.2014.01.032.


Copyright (c) 2017 Anindita Mukherjee, Rana Chatterjee, Aramita De, Satyajit Samanta, Sachinta Mahato, Nirnita Chakraborty Ghosal, G. V. Zyryanov, Adinath Majee

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Chimica Techno Acta, 2014-2022
ISSN 2411-1414 (Online)