Asymmetric Direct Aldol Reaction Catalyzed by (1R, 2R)-(+)-1, 2- Diammonium Cyclohexane-L-tartrate in Water

Author(s): Anirban Mondal, Kartick Chandra Bhowmick*.

Journal Name: Current Organocatalysis

Volume 6 , Issue 2 , 2019

Become EABM
Become Reviewer

Graphical Abstract:


Abstract:

Background: A cheap and commercially available organocatalyst, (1R, 2R)-(+)-1, 2- diammonium cyclohexane-L-tartrate 1 was applied in direct aldol reaction in water. The organocatalyst 1 afforded aldol products from cyclohexanone and substituted aromatic aldehydes with high yield (up to 90%) and good stereoselectivity (up to 99% ee and up to 11.5:1 dr) in large volume of water (10 ml).

Methods: The same aldol reaction when carried out in the presence of more expensive organocatalyst e.g. (1R, 2R)-(+)-1,2-diaminocyclohexane and 1,6-hexanediaoic acid as acid additive furnished the aldol products with only 20% yield, 2:1 anti/syn ratio and 92% ee.

Results and Conclusion: In summary, we have applied a reasonably cheap and commercially available organocatalyst 1 for highly enantioselective direct aldol reaction in water at room temperature.

Keywords: 1, 2-diaminocyclohexane-L-tartrate, 1, 6-hexanediaoic acid, asymmetric aldol reaction, cyclohexanone, organocatalysis, enantioaselective, water.

[1]
List, B.; Lerner, R.A.; Barbas III, C.F. Proline catalyzed direct asymmetric aldol reactions. J. Am. Chem. Soc., 2000, 122, 2395-2396.
[2]
Ahrendt, K.A.; Borths, C.J.; MacMillan, D.W.C. New strategies for organic catalysis: the first highly enantioselective organocatalytic Diels-Alder reaction. J. Am. Chem. Soc., 2000, 122, 4243-4244.
[3]
Hajos, Z.G.; Parrish, D.R. Asymmetric synthesis of bicyclic intermediates of natural product chemistry. J. Org. Chem., 1974, 39, 1615-1621.
[4]
Bhowmick, S.; Bhowmick, K.C. Catalytic asymmetric carbon–carbon bond-forming reactions in aqueous media. Tetrahedron Asymmetry, 2011, 22, 1945-1979.
[5]
Heravi, M.M.; Zadsirjan, V.; Dehghani, M.; Hosseintash, N. Current applications of organocatalysts in asymmetric aldol reactions: An update. Tetrahedron Asymmetry, 2017, 28, 587-707.
[6]
Li, Z. -.Y.; Chen, Y.; Zheng, C.-Q.; Yin, Y.; Wang, L.; Sun, X.-Q. Highly enantioselective aldol reactions catalyzed by reusable upper rim-functionalized calix[4]arene-based L-proline organocatalyst in aqueous conditions. Tetrahedron, 2017, 73, 78-85.
[7]
Bisticha, A.; Triandafillidi, I.; Kokotos, C.G. tert-Butyl esters of peptides as organocatalysts for the asymmetric aldol reaction. Tetrahedron Asymmetry, 2015, 26, 102-108.
[8]
Cabrera, H.R.; Huelgas, G.; Pérez, J.M.H.; Patrick, J. Walsh, P.J.; Somanathan, R.; Parrodi, C.A. Homochiral L-prolinamido-sulfonamides and their use as organocatalysts in aldol reactions. Tetrahedron Asymmetry, 2015, 26, 163-172.
[9]
Rambo, R.S.; Jacoby, C.G.; Silva, T.L.; Schneider, P.H. A highly enantio- and diastereoselective direct aldol reaction in aqueous medium catalyzed by thiazolidine-based compounds. Tetrahedron Asymmetry, 2015, 26, 632-637.
[10]
Guo, G.; Wub, Y.; Zhao, X.; Wang, J.; Zhang, L.; Cui, Y. Polymerization of L-proline functionalized styrene and its catalytic performance as a supported organocatalyst for direct enantioselective aldol reaction. Tetrahedron Asymmetry, 2016, 27, 740-746.
[11]
Gurka, A.A.; Szori, K.; Bartók, M.; London, G. Dual stereocontrol in aldol reactions catalysed by hydroxyproline derivatives in the presence of a large amount of water. Tetrahedron Asymmetry, 2016, 27, 936-942.
[12]
Sahin, O.; Eymur, S.; Uyanik, A.; Akceylan, E.; Yilmaz, M. Chiral calix[4]arenes-bearing prolinamide functionality as organocatalyst for asymmetric direct aldol reactions in water. Polycycl. Aromat. Compd., 2016, 36, 168-179.
[13]
Obregón-Zúñiga, A.; Juaristi, E. (2S,4R)-Hyp-(S)-Phe-OMe dipeptide supported on imidazolium tagged molecules as recoverable organocatalysts for asymmetric aldol reactions using water as reaction medium. Tetrahedron, 2017, 73, 5373-5380.
[14]
Bhowmick, S.; Mondal, A.; Ghosh, A.; Bhowmick, K.C. Water: the most versatile and nature′s friendly media in asymmetric organocatalyzed direct aldol reactions. Tetrahedron Asymmetry, 2015, 26, 1215-1244.
[15]
Ghosh, A.; Bhowmick, S.; Mondal, A.; Garai, H.; Bhowmick, K.C. Advances on asymmetric organocatalyzed mannich reactions in aqueous and non-aqueous media. COCAT, 2016, 3, 133-160.
[16]
Mondal, A.; Bhowmick, S.; Ghosh, A.; Chanda, T.; Bhowmick, K.C. Advances on asymmetric organocatalytic 1, 4-conjugate addition reactions in aqueous and semi-aqueous media. Tetrahedron Asymmetry, 2017, 28, 849-875.
[17]
Bhowmick, S.; Kunte, S.S.; Bhowmick, K.C. The smallest organocatalyst in highly enantioselective direct aldol reaction in wet solvent-free conditions. RSC Advances, 2014, 4, 24311-24315.
[18]
Bhowmick, S.; Kunte, S.S.; Bhowmick, K.C. A new organocatalyst derived from abietic acid and 4-hydroxy-l-proline for direct asymmetric aldol reactins in aqueous media. Tetrahedron Asymmetry, 2014, 25, 1292-1297.
[19]
Bhowmick, K.C.; Chanda, T. Chapter 12: Asymmetric organocatalysis in aqueous media. in green techniques for organic synthesis and medicinal chemistry, (2nd Edn); Zhang, W.; Cue, B.W. Eds.; John Wiley & Sons Ltd.: New Jersey, USA,. 2018, 291-324.
[20]
Mondal, A.; Bhowmick, K.C. The carbamate esters as organocatalysts in asymmetric michael addition reactions in aqueous media: when pyrrolidine backbone surpasses 1,2-diaminocyclohexane. ARKIVOC, 2018, 320-331.
[21]
Ahmetlli, A.; Spiliopoulou, N.; Magi-Oikonomopoulou, A.; Gerokonstantis, D-T.; Moutevelis-Minakakis, P.; Kokotos, C.G. Proline dipeptides containing fluorine moieties as oganocatalysts for the asymmetric aldol reaction. Tetrahedron, 2018, 74, 5987-5995.
[22]
Bhati, M.; Kumari, K.; Easwar, S. Probing the synergistic catalytic model: a rationally designed urea-tagged proline catalyst for the direct asymmetric aldol reaction. J. Org. Chem., 2018, 83, 8225-8232.
[23]
Obregón-Zúñiga, A.; Milán, M.; Juaristi, E. Improving the catalytic performance of (s)-proline as organocatalyst in asymmetric aldol reactions in the presence of solvate ionic liquids: involvement of a supramolecular aggregate. Org. Lett., 2017, 19, 1108-1111.
[24]
Duss, M.; Manni, L.S.; Moser, L.; Handschin, S.; Mezzenga, R.; Jessen, H.J.; Landau, E.M. Lipidic mesophases as novel nanoreactor scaffolds for organocatalysts: heterogeneously catalysed asymmetric aldol reactions in confined water. ACS Appl. Mater. Interfaces, 2018, 10, 5114-5124.
[25]
Zhou, L.; Chu, B-F.; Xu, X-Y.; Xu, L.; Liu, N.; Wu, Z-Q. Significant improvement on enantioselectivity and diastereoselectivity of organocatalyzed asymmetric aldol reaction using helical polyisocyanides bearing proline pendants. ACS Macro Lett., 2017, 6, 824-829.
[26]
Nobakht, Y.; Arshadi, N. DFT study of the dual catalytic role of L-proline in the aldol reaction and the effect of water on it. J. Mol. Model., 2018, 24, 334-344.
[27]
Liu, K.; Ye, L.; Wang, Y.; Du, G.; Jiang, L. A pseudopeptide polymer micelle used for asymmetric catalysis of the aldol reaction in water. Polymers , 2018, 10, 1004-1015.
[28]
Liu, Y.; Wang, J.; Sun, Q.; Li, R. Chiral 1, 2-diaminocyclohexane as organocatalyst for enantioselective aldol reaction. Tetrahedron Lett., 2011, 52, 3584-3587.
[29]
Bhowmick, S.; Kunte, S.S.; Bhowmick, K.C. A comprehensive study on the effect of acid additives in 1(R), 2(R)-Bis [(S)-prolinamido] cyclohexane catalyzed direct asymmetric aldol reactions in aqueous media. Indian J. Chem., 2015, 54B, 84-92.
[30]
Triandafillidi, I.; Bisticha, A.; Voutyritsa, E.; Galiatsatou, G.; Kokotos, C.G. tert-Butyl ester or benzylamide of the dipeptide Pro-Gly as organocatalysts for the asymmetric aldol reaction. Tetrahedron, 2015, 71, 932-940.
[31]
Machuca, E.; Rojas, Y.; Juaristi, E. Synthesis and evaluation of (s)-proline-containing α, β-dipeptides as organocatalysts in solvent-free asymmetric aldol reactions under ball-milling conditions. Asian J. Org. Chem., 2015, 4, 46-53.
[32]
Yadav, G.D.; Singh, S. Direct asymmetric aldol reactions catalysed by trans-4-hydroxy-(S)-prolinamide in solvent-free conditions. Tetrahedron Asymmetry, 2015, 26, 1156-1166.


Rights & PermissionsPrintExport Cite as

Article Details

VOLUME: 6
ISSUE: 2
Year: 2019
Page: [165 - 170]
Pages: 6
DOI: 10.2174/2213337206666181227151140

Article Metrics

PDF: 13
HTML: 5
EPUB: 1
PRC: 1

Special-new-year-discount