Abstract
α-Substituted α,β-unsaturated aldehydes represent a highly reactive class of compounds with a broad scope of application. Therefore, the development of methods for the synthesis of these bifunctional compounds is a dynamically progressing area of research. This review summarizes and highlights methods for the synthesis of α-alkyl α,β-alkenals.
Keywords: Aldol reactions, organocatalysis, α -alkyl α, β-alkenals, α, β-unsaturated aldehydes, unsaturated heteroatomic compounds, organic synthesis.
Graphical Abstract
[1]
Keiko, N.A.; Voronkov, M.G. αα-Functionalized α,β-unsaturated
aldehydes. J. All-Union Chem. Soc., 1991, 468-475.
[2]
(a) Fahlbusch, K.H.; Hammerschmidt, F.-J.; Panten, J.; Pickenhagen, W.; Schatkowski, D.; Bauer, K.; Garbe, D.; Surburg, H. Flavors and Fragrances. Ullmann’s Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH: Weinheim, 2002.
(b) Sharma, S.K.; Srivastava, V.K.; Shukla, R.S.; Parikh, P.A.; Jasra, R.V. One pot synthesis of C8 aldehydes/alcohols from propylene using eco-friendly hydrotalcite supported HRhCO(PPh3)3 catalyst. New J. Chem., 2007, 31, 277-286.
(c) Jose, T.; Sudheesh, N.; Shukla, R.S. Amino functionalized chitosan as a catalyst for selective solvent free self-condensation of linear aldehydes. J. Mol. Catal. Chem., 2010, 333, 158-166.
(b) Sharma, S.K.; Srivastava, V.K.; Shukla, R.S.; Parikh, P.A.; Jasra, R.V. One pot synthesis of C8 aldehydes/alcohols from propylene using eco-friendly hydrotalcite supported HRhCO(PPh3)3 catalyst. New J. Chem., 2007, 31, 277-286.
(c) Jose, T.; Sudheesh, N.; Shukla, R.S. Amino functionalized chitosan as a catalyst for selective solvent free self-condensation of linear aldehydes. J. Mol. Catal. Chem., 2010, 333, 158-166.
[3]
(a) Kim, H.; Ralph, J.; Lu, F. Ralph, Sally A. NMR analysis of lignins in CAD-deficient plants. Incorporation of hydroxycinnamaldehydes and hydroxybenzaldehydes into lignins. Org. Biomol. Chem., 2003, 1, 268-281.
(b) Sy, L.K.; Brown, G.D. Coniferaldehyde derivatives from tissue culture of Artemisia annua and Tanacetum parthenium. Phytochemistry, 1999, 50, 781-785.
(c) Strunz, G.M.; Bethell, R.; Sampson, G.; White, P. On the Baylis-Hillman reaction of acrylate, acrylonitrile, and acrolein with some non-enolizable α-dicarbonyl compounds: Synthesis of phytotoxic bipolaroxin models. Can. J. Chem., 1995, 73, 1611-1674.
(d) Schneider, J.A.; Nakanishi, K. A new class of sweet potato phytoalexins. J. Chem. Soc. Chem. Commun., 1983, 7, 353-355.
(b) Sy, L.K.; Brown, G.D. Coniferaldehyde derivatives from tissue culture of Artemisia annua and Tanacetum parthenium. Phytochemistry, 1999, 50, 781-785.
(c) Strunz, G.M.; Bethell, R.; Sampson, G.; White, P. On the Baylis-Hillman reaction of acrylate, acrylonitrile, and acrolein with some non-enolizable α-dicarbonyl compounds: Synthesis of phytotoxic bipolaroxin models. Can. J. Chem., 1995, 73, 1611-1674.
(d) Schneider, J.A.; Nakanishi, K. A new class of sweet potato phytoalexins. J. Chem. Soc. Chem. Commun., 1983, 7, 353-355.
[4]
(a) Boerth, D.W.; Eder, E.; Hussain, S.; Hoffman, C. Structures of acrolein-guanine adducts: A semi-empirical self-consistent field and nuclear magnetic resonance spectral study. Chem. Res. Toxicol., 1998, 11(4), 284-294.
(b) Robert, F.; Héritier, J.; Quiquerez, J.; Simian, H.; Blank, I. Synthesis and sensorial properties of 2-alkylalk-2-enals and 3-(acetylthio)-2-alkyl alkanals. J. Agric. Food Chem., 2004, 52(11), 3525-3529.
(b) Robert, F.; Héritier, J.; Quiquerez, J.; Simian, H.; Blank, I. Synthesis and sensorial properties of 2-alkylalk-2-enals and 3-(acetylthio)-2-alkyl alkanals. J. Agric. Food Chem., 2004, 52(11), 3525-3529.
[5]
(a) Keiko, N.A.; Vchislo, V. Synthesis of diheteroatomic five membered heterocyclic compounds from α,β-unsaturated aldehydes. Asian J. Org. Chem., 2016, 5, 1169-1197.
(b) Keiko, N.A.; Vchislo, N.V. α,β‐Unsaturated aldehydes in the synthesis of five‐membered heterocyclic compounds with one heteroatom: Recent advances from developments in metal‐ and organocatalysis. Asian J. Org. Chem., 2016, 5, 439-461.
(b) Keiko, N.A.; Vchislo, N.V. α,β‐Unsaturated aldehydes in the synthesis of five‐membered heterocyclic compounds with one heteroatom: Recent advances from developments in metal‐ and organocatalysis. Asian J. Org. Chem., 2016, 5, 439-461.
[6]
(a) Wei, Y; Tang, J.; Cong, X.; Zeng, X. Practical metal-free synthesis of chalcone derivatives via a tandem cross-dehydrogenative coupling/ elimination reaction. Green Chem., 2013, 15, 3165-3169.
(b) Noble, A; Anderson, J.C. Nitro-Mannich reaction. Chem. Rev., 2013, 113(5), 2887-2939.
(b) Noble, A; Anderson, J.C. Nitro-Mannich reaction. Chem. Rev., 2013, 113(5), 2887-2939.
[7]
(a) Trost, B.M; Brindle, C.S. The direct catalytic asymmetric aldol reaction. Chem. Soc. Rev., 2010, 39(5), 1600-1632.
(b) Giacalone, F.; Gruttadauria, M.; Agrigento, P.; Noto, R. Low-loading asymmetric organocatalysis. Chem. Soc. Rev., 2012, 41(6), 2406-2447.
(c) Alemán, J.; Cabrera, S Applications of asymmetric organocatalysis in medicinal chemistry. Chem. Soc. Rev., 2013, 42(2), 774-793.
(b) Giacalone, F.; Gruttadauria, M.; Agrigento, P.; Noto, R. Low-loading asymmetric organocatalysis. Chem. Soc. Rev., 2012, 41(6), 2406-2447.
(c) Alemán, J.; Cabrera, S Applications of asymmetric organocatalysis in medicinal chemistry. Chem. Soc. Rev., 2013, 42(2), 774-793.
[8]
(a) Córdova, A The direct catalytic asymmetric mannich reaction. Acc. Chem. Res., 2004, 37(2), 102-112.
(b) Verkade, J.M.M.; van Hemert, L.J.C.; Quaedflieg, P.J.L.M.; Rutjes, F.P.J.T. Organocatalysed asymmetric Mannich reactions. Chem. Soc. Rev., 2008, 37(1), 29-41.
(c) Cai, X-H.; Xie, B. Recent advances on organocatalysed asymmetric Mannich reactions. ARKIVOC, 2013, i, 264-293.
(b) Verkade, J.M.M.; van Hemert, L.J.C.; Quaedflieg, P.J.L.M.; Rutjes, F.P.J.T. Organocatalysed asymmetric Mannich reactions. Chem. Soc. Rev., 2008, 37(1), 29-41.
(c) Cai, X-H.; Xie, B. Recent advances on organocatalysed asymmetric Mannich reactions. ARKIVOC, 2013, i, 264-293.
[9]
Wittig methodologies represent another interesting root to directly prepare α,β-unsaturated aldehydes; see also:. (a) Reid, M.; Rowe, D.J.; Taylor, R.J.K. Two carbon homologated α,β-unsaturated aldehydes from alcohols using the in situ oxidation-Wittig reaction. Chem. Comm., 2003, 2284-2285.
(b) McNulty, J.; Zepeda Velazquez, C.; McLeod, D. Development of a robust reagent for the two-carbon homologation of aldehydes to (E)-α,β-unsaturated aldehydes in water. Green Chem., 2013, 15, 15-3149.
(b) McNulty, J.; Zepeda Velazquez, C.; McLeod, D. Development of a robust reagent for the two-carbon homologation of aldehydes to (E)-α,β-unsaturated aldehydes in water. Green Chem., 2013, 15, 15-3149.
[10]
(a) Casalea, M.T.; Richmana, A.R.; Elroda, M.J.; Garland, R.M.; Beaver, M.R.; Tolbert, M.A. Kinetics of acid-catalyzed aldol condensation reactions of aliphatic aldehydes. Atmos. Environ., 2007, 41, 6212-6224.
(b) Mandal, S.; Mandal, S.; Ghosh, S.K.; Ghosh, A.; Saha, R.; Banerjies, S.; Saha, B. Review of the aldol reaction. Synth. Commun., 2016, 46, 1327-1342.
(b) Mandal, S.; Mandal, S.; Ghosh, S.K.; Ghosh, A.; Saha, R.; Banerjies, S.; Saha, B. Review of the aldol reaction. Synth. Commun., 2016, 46, 1327-1342.
[11]
Shimizu, K.; Hayashi, E.; Inokuchi, T.; Kodama, T.; Hagiwara, H.; Kitayama, Y. Self-aldol condensation of unmodified aldehydes catalysed by secondary-amine immobilised in FSM-16 silica. Tetrahedron Lett., 2002, 43, 9073-9075.
[http://dx.doi.org/10.1016/S0040-4039(02)02313-4]
[http://dx.doi.org/10.1016/S0040-4039(02)02313-4]
[12]
(a) Weirzechowski, P.T.; Zatarski, L.W. Aldol condensation in gaseous phase by zeolite catalysts. Catal. Lett., 1991, 9, 411-414.
(b) Sharma, S.K.; Parikh, P.A.; Jasra, R.V. Eco-friendly synthesis of jasminaldehyde by condensation of 1-heptanal with benzaldehyde using hydrotalcite as a solid base catalyst. J. Mol. Catal. Chem., 2008, 286, 55-62.
(c) Sharma, S.K.; Patel, H.A.; Jasra, R.V. Synthesis of jasmin-aldehyde using magnesium organo silicate as a solid base catalyst. J. Mol. Catal. Chem., 2008, 280, 61-67.
(d) Kitazume, T.; Nagura, H.; Koguchi, S. One step synthesis of 2-substituted 3-tri-(or di-)fluoromethyl-2-propenals in an ionic liquid. J. Fluor. Chem., 2004, 125, 79-82.
(b) Sharma, S.K.; Parikh, P.A.; Jasra, R.V. Eco-friendly synthesis of jasminaldehyde by condensation of 1-heptanal with benzaldehyde using hydrotalcite as a solid base catalyst. J. Mol. Catal. Chem., 2008, 286, 55-62.
(c) Sharma, S.K.; Patel, H.A.; Jasra, R.V. Synthesis of jasmin-aldehyde using magnesium organo silicate as a solid base catalyst. J. Mol. Catal. Chem., 2008, 280, 61-67.
(d) Kitazume, T.; Nagura, H.; Koguchi, S. One step synthesis of 2-substituted 3-tri-(or di-)fluoromethyl-2-propenals in an ionic liquid. J. Fluor. Chem., 2004, 125, 79-82.
[13]
Jose, T.; Sudheesh, N.; Shukla, R.S. Amino functionalized chitosan as a catalyst for selective solvent-free self-condensation of linear aldehydes. J. Mol. Catal. Chem., 2010, 333, 158-166.
[http://dx.doi.org/10.1016/j.molcata.2010.10.012]
[http://dx.doi.org/10.1016/j.molcata.2010.10.012]
[14]
Hamaya, J.; Suzuki, T.; Hoshi, T.; Shimizu, K.; Kitayama, Y.; Hagiwara, H. Sustainable self-aldol condensation jun of unmodified aldehyade: a combination of ionic liquid and heterogeneous secondary-amine grafted on silica. Synlett, 2003, 6, 873-875.
[15]
Cota, Iu.; Chimentao, R.; Sueiras, J.; Medina, F. The DBU-H2O complex as a new catalyst for aldol condensation reactions. Catal. Commun., 2008, 9, 2090-2094.
[http://dx.doi.org/10.1016/j.catcom.2008.03.047]
[http://dx.doi.org/10.1016/j.catcom.2008.03.047]
[16]
Watanabe, Y.; Sawada, K.; Hayashi, M. A green method for the self-aldol condensation of aldehydes using lysine. Green Chem., 2010, 12, 384-386.
[http://dx.doi.org/10.1039/b918349c]
[http://dx.doi.org/10.1039/b918349c]
[17]
Deshpande, R.M.; Diwakar, M.M.; Mahajan, A.N.; Chaudhari, R.V. Biphasic catalysis for a selective oxo–Mannich tandem synthesis of methacrolein. J. Mol. Catal. A., 2004, 211, 49-53.
[http://dx.doi.org/10.1016/j.molcata.2003.10.010]
[http://dx.doi.org/10.1016/j.molcata.2003.10.010]
[18]
(a) Erkkilä, A.; Pihko, P.M. Rapid organocatalytic aldehyde aldehyde condensation reactions. Eur. J. Org. Chem., 2007, 4205-4216.
(b) Erkkilä, A.; Pihko, P.M. Mild organocatalytic α-methylenation of aldehydes. J. Org. Chem., 2006, 71(6), 2538-2541.
(b) Erkkilä, A.; Pihko, P.M. Mild organocatalytic α-methylenation of aldehydes. J. Org. Chem., 2006, 71(6), 2538-2541.
[19]
Limnios, D.; Kokotos, C.G. Microwave-assisted organocatalytic cross-aldolcondensation of aldehydes. RSC Advances, 2013, 3, 4496-4499.
[http://dx.doi.org/10.1039/c3ra00114h]
[http://dx.doi.org/10.1039/c3ra00114h]
[20]
Surburg, H.; Panten, J. Common Fragrance and Flavor Materials:
Preperation; Properties and Uses; Wiley-VCH Verlag GmbH &
Co. KGaA: Weinheim, 2006.
[http://dx.doi.org/10.1002/3527608214]
[http://dx.doi.org/10.1002/3527608214]
[21]
Fang, X.; Jackstell, R.; Franke, R.; Beller, M. Domino hydroformylation/aldol condensation catalysis: Highly selective synthesis of α,β-unsaturated aldehydes from olefins. Chemistry, 2014, 20(41), 13210-13216.
[http://dx.doi.org/10.1002/chem.201403302] [PMID: 25179918]
[http://dx.doi.org/10.1002/chem.201403302] [PMID: 25179918]
[22]
Mura, M.G.; De Luca, L.; Taddei, M.; Williams, J.M.J.; Porcheddu, A. Synthesis of α,β-unsaturated aldehydes based on a one-pot phase-switch dehydrogenative cross-coupling of primary alcohols. Org. Lett., 2014, 16(10), 2586-2589.
[http://dx.doi.org/10.1021/ol500916g] [PMID: 24787700]
[http://dx.doi.org/10.1021/ol500916g] [PMID: 24787700]
[23]
Lahmar, N.; Aatar, J.; Ayed, T.B.; Amri, H.; Bellassoued, M. A general route to α-alkyl (E)-α,β-unsaturated aldehydes. J. Organomet. Chem., 2006, 691, 3018-3026.
[http://dx.doi.org/10.1016/j.jorganchem.2006.03.015]
[http://dx.doi.org/10.1016/j.jorganchem.2006.03.015]
[24]
Fearnley, S.T.; Funk, R.L. Gregg, R.J. Preparation of 2-alkyl- and 2-acylpropenals from 5-(trifluoromethanesulfonyloxy)-4H-1,3-dioxin: A versatile acrolein α-cation synthon. Tetrahedron, 2000, 56, 10275-10281.
[http://dx.doi.org/10.1016/S0040-4020(00)00872-3]
[http://dx.doi.org/10.1016/S0040-4020(00)00872-3]
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