Generic placeholder image

Current Organocatalysis

Editor-in-Chief

ISSN (Print): 2213-3372
ISSN (Online): 2213-3380

Research Article

Synthesis of 1,2-Diamine Bifunctional Catalysts for the Direct Aldol Reaction Through Probing the Remote Amide Hydrogen

Author(s): Rajasekhar Dodda, Sampak Samanta, Matthew Su and John Cong-Gui Zhao*

Volume 6, Issue 2, 2019

Page: [171 - 176] Pages: 6

DOI: 10.2174/2213337206666190301155247

Abstract

Background: While proline can catalyze the asymmetric direct aldol reactions, its catalytic activity and catalyst turnover are both low. To improve the catalytic efficiency, many prolinebased organocatalysts have been developed. In this regard, prolinamide-based bifunctional catalysts have been demonstrated by us and others to be highly efficient catalysts for the direct aldol reactions.

Results: Using the β-acetamido- and β-tosylamidoprolinamide catalysts, the highly enantio- and diastereoselective direct aldol reactions between enolizable ketones and aldehydes were achieved (up to >99% ee, 98:2 dr). A low catalyst loading of only 2-5 mol % of the β-tosylamidoprolinamide catalyst was needed to obtain the desired aldol products in good to high yields and high stereoselectivities.

Methods: By carefully adjusting the hydrogen bonding ability of the remote β-amide hydrogen of the 1,2-diamine-based prolinamide bifunctional catalysts, the catalytic activity and the asymmetric induction of these catalysts were significantly improved for the direct aldol reaction between aldehydes and enolizable ketones.

Conclusion: Some highly efficient 1,2-diamine-based bifunctional prolinamide catalysts have been developed through probing the remote β-amide hydrogen for its hydrogen bonding capability. These catalysts are easy to synthesize and high enantioselectivities may be achieved at very low catalyst loadings.

Keywords: Aldol, amide, asymmetric, bifunctional, catalysis, hydrogen bonding, proline.

Graphical Abstract

[1]
Kim, B.M.; Williams, S.F.; Masamune, S. In: Comprehensive Organic Synthesis; Trost, B.M.; Fleming, I.; Heathcock, C.H., Eds.; Pergamon: Oxford, 1991, Vol. 2, pp. 229-275.
[2]
Eder, U.; Sauer, G.; Wiechert, R. New type of asymmetric cyclization to optically active steroid CD partial structures. Angew. Chem. Int. Ed. Engl., 1971, 10, 496-497.
[3]
Hajos, Z.G.; Parrish, D.R. Asymmetric synthesis of bicyclic intermediates of natural product chemistry. J. Org. Chem., 1974, 39, 1615-1621.
[4]
List, B.; Lerner, R.A.; Barbas III, C.F. Proline-catalyzed direct asymmetric aldol reactions. J. Am. Chem. Soc., 2000, 122, 2395-2396.
[5]
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.
[6]
Enantioselective Organocatalysis, Reactions and Experimental Procedures;; Dalko, P.I. Ed.; Wiley-VCH: Weinheim,. , 2007.
[7]
Asymmetric Organocatalysis, From Biomimetic Concepts to Applications in Asymmetric Synthesis;; Berkessel, A.; Gröger, H. Eds.; Wiley-VCH: Weinheim,. , 2005.
[8]
Comprehensive Enantioselective Organocatalysis: Catalysts, Reactions, and Applications; Dalko, P.I. Ed.; Wiley-VCH: Weinheim,. , 2013.
[9]
Notz, W.; List, B. Catalytic asymmetric synthesis of anti-1,2-diols. J. Am. Chem. Soc., 2000, 122, 7386-7387.
[10]
Sakthivel, K.; Notz, W.; Bui, T.; Barbas III, C.F. Amino acid catalyzed direct asymmetric aldol reactions: A bioorganic approach to catalytic asymmetric carbon-carbon bond-forming reactions. J. Am. Chem. Soc., 2001, 123, 5260-5267.
[11]
List, B. Enamine catalysis is a powerful strategy for the catalytic generation and use of carbanion equivalents. Acc. Chem. Res., 2004, 37, 548-557.
[12]
Notz, W.; Tanaka, F.; Barbas III, C.F. Enamine-based organocatalysis with proline and diamines: The development of direct catalytic asymmetric aldol, Mannich, Michael, and Diels-Alder Reactions. Acc. Chem. Res., 2004, 37, 580-591.
[13]
List, B. Proline-catalyzed asymmetric reactions. Tetrahedron, 2002, 58, 5573-5590.
[14]
Bisai, V.; Bisai, A.; Singh, V.K. Enantioselective organocatalytic aldol reaction using small organic molecules. Tetrahedron, 2012, 68, 4541-4580.
[15]
Trost, B.M.; Brindle, C.S. The direct catalytic asymmetric aldol reaction. Chem. Soc. Rev., 2010, 39, 1600-1632.
[16]
Pellissier, H. Asymmetric organocatalysis. Tetrahedron, 2007, 63, 9267-9331.
[17]
Guillena, G. Organocatalyzed aldol reactions. In: Modern Methods in Stereoselective Aldol Reactions; Mahrwald, R., Ed.; Wiley-VCH: Weinheim, 2013, pp. 155-268.
[18]
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.
[19]
Tang, Z.; Jiang, F.; Yu, L-T.; Gong, L-Z.; Mi, A-Q.; Jiang, Y-Z.; Wu, Y-D. Novel small organic molecules for a highly enantioselective direct aldol reaction. J. Am. Chem. Soc., 2003, 125, 5262-5263.
[20]
Tang, Z.; Jiang, F.; Cui, X.; Gong, L-Z.; Mi, A-Q.; Jiang, Y-Z.; Wu, Y-D. Enantioselective direct aldol reactions catalyzed by L-prolinamide derivatives. Proc. Natl. Acad. Sci. USA, 2004, 101, 5755-5760.
[21]
Tang, Z.; Yang, Z-H.; Chen, X-H.; Cun, L-F.; Mi, A-Q.; Jiang, Y-Z.; Gong, L-Z. A highly efficient organocatalyst for direct aldol reactions of ketones with aldedydes. J. Am. Chem. Soc., 2005, 127, 9285-9289.
[22]
Samanta, S.; Liu, J.; Dodda, R.; Zhao, C-G. C2-symmetric bisprolinamide as a highly efficient catalyst for direct aldol reaction. Org. Lett., 2005, 7, 5321-5323.
[23]
Chen, J-R.; Lu, H-H.; Li, X-Y.; Chen, L.; Wan, J.; Xiao, W-J. Readily tunable and bifunctional L-prolinamide derivatives: Design and application in the direct enantioselective aldol reactions. Org. Lett., 2005, 7, 4543-4545.
[24]
Chen, J-R.; Li, X-Y.; Xing, X-N.; Xiao, W-J. Sterically and electronically tunable and bifunctional organocatalysts: Design and application in asymmetric aldol reaction of cyclic ketones with aldehydes. J. Org. Chem., 2006, 71, 8198-8202.
[25]
Chen, J-R.; An, X-L.; Zhu, X-Y.; Wang, X-F.; Xiao, W-J. Rational combination of two privileged chiral backbones: Highly efficient organocatalysts for asymmetric direct aldol reactions between aromatic aldehydes and acylic ketones. J. Org. Chem., 2008, 73, 6006-6009.
[26]
Gandhi, S.; Singh, V.K. Synthesis of chiral organocatalysts derived from aziridines: Application in asymmetric aldol reaction. J. Org. Chem., 2008, 73, 9411-9416.
[27]
Rojas Cabrera, H.; Huelgas, G.; Hernandez Perez, J.M.; Walsh, P.J.; Somanathan, R.; Anaya de Parrodi, C. Homochiral L-prolinamido-sulfonamides and their use as organocatalysts in aldol reactions. Tetrahedron Asymmetry, 2015, 26, 163-172.
[28]
Kucherenko, A.S.; Syutkin, D.E.; Zlotin, S.G. Asymmetric aldol condensation in an ionic liquid-water system catalyzed by (S)-prolinamide derivatives. Russ. Chem. Bull. Int. Ed., 2008, 57, 59-594.
[29]
Chen, F.; Huang, S.; Zhang, H.; Liu, F.; Peng, Y. Proline-based dipeptides with two amide units as organocatalyst for the asymmetric aldol reaction of cyclohexanone with aldehydes. Tetrahedron, 2008, 64, 9585-9591.
[30]
Maleev, V.I.; Gugkaeva, Z.T.; Moskalenko, M.A.; Tsaloev, A.T.; Lyssenko, K.A. New (S)-proline derivatives as catalysts for the enantioselective aldol reaction. Russ. Chem. Bull. Int. Ed, 2009, 58, 1903-1907.
[31]
De Nisco, M.; Pedatella, S.; Ullah, H.; Zaidi, J.H.; Naviglio, D.; Özdamar, O.; Caputo, R. Proline−β3-amino-ester dipeptides as efficient catalysts for enantioselective direct aldol reaction in aqueous medium. J. Org. Chem., 2009, 74, 9562-9565.
[32]
Tzeng, Z-H.; Chen, H-Y.; Reddy, R-J.; Huang, C-T.; Chen, K. Highly diastereo- and enantioselective direct aldol reactions promoted by water-compatible organocatalysts bearing a pyrrolidinyl-camphor structural scaffold. Tetrahedron, 2009, 65, 2879-2888.
[33]
Yang, Y.; He, Y-H.; Guan, Z.; Huang, W-D. A highly efficient large-scale asymmetric direct intermolecular aldol reaction employing L-prolinamide as a recoverable catalyst. Adv. Synth. Catal., 2010, 352, 2579-2587.
[34]
Saha, S.; Moorthy, J.N. Highly enantioselective aldol reactions using N-arylprolinamides with enhanced acidity and double H-bonding potential. Tetrahedron Lett., 2010, 51, 912-916.
[35]
Subba Reddy, B.V.; Bhavani, K.; Raju, A.; Yadav, J.S. A novel trifunctional organocatalyst for the asymmetric aldol reaction: a facile enantioselective synthesis of β-hydroxyketones. Tetrahedron Asymmetry, 2011, 22, 881-886.
[36]
Hernández, J.G.; García-López, V.; Juaristi, E. Solvent-free asymmetric aldol reaction organocatalyzed by (S)-proline-containing thiodipeptides under ball-milling conditions.-. Tetrahedron, 2012, 68, 92-97.
[37]
Sutar, R.L.; Joshi, N.N. Systematic evaluation of a few proline derivatives as catalysts for a direct aldol reaction. Tetrahedron Asymmetry, 2013, 24, 43-49.
[38]
Bañón-Caballero, A.; Guillena, G.; Nájera, C.; Faggi, E.; Sebastián, R.M.; Vallribera, A. Recoverable silica-gel supported binam-prolinamides as organocatalysts for the enantioselective solvent-free intra- and intermolecular aldol reaction. Tetrahedron, 2013, 69, 1307-1315.
[39]
Pedrosa, R.; Andrés, J.M.; Gamarra, A.; Manzano, R.; Pérez-López, C. Novel sulfonylpolystyrene-supported prolinamides as catalysts for enantioselective aldol reaction in water. Tetrahedron, 2013, 69, 10811-10819.
[40]
Samanta, S.; Zhao, C-G. Asymmetric direct aldol reaction of 1,2-diketones and ketones mediated by proline derivatives. Tetrahedron Lett., 2006, 47, 3383-3386.
[41]
Mitchell, J.M.; Finney, N.S. An efficient method for the preparation of N, N-disubstituted 1, 2-diamines. Tetrahedron Lett., 2000, 41, 8431-8434.
[42]
Xu, D.; Prasad, K.; Repic, O.; Blacklock, T.J. Ethyl trifluoroacetate: a powerful reagent for differentiating amino groups. Tetrahedron Lett., 1995, 36, 7357-7360.
[43]
Manville, C.V.; Docherty, G.; Padda, R.; Wills, M. Application of proline-functionalized 1,2-diphenylethane-1,2-diamine (DPEN) in asymmetric transfer hydrogenation of ketones. Eur. J. Org. Chem., 2011, 6893-6901.

Rights & Permissions Print Cite
© 2024 Bentham Science Publishers | Privacy Policy