Abstract
Ca(OTf)2/Bu4NPF6 catalytic system has been illustrated for the synthesis of Diels–Alder adduct for the first time. This procedure tolerates substrate diversity and delivers high yield. Use of environmentally benign catalyst, high yields and substrate diversity are the highlight of the existing method.
Graphic Abstract
Ca(OTf)2, along with n-Bu4NPF6 as the co-catalyst, is shown to be an effective Lewis acidic catalyst system for the Diels–Alder reaction. Apart from being sustainable and efficient, this procedure is robust and products are obtained in near-quantitative yields.
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References
- 1.
Diels O and Alder K 1928 Synthesen in der hydroaromatischen Reihe Justus Liebigs Ann. Chem. 460 98
- 2.
Dewar M J S, Olivella S and Stewart J J P 1986 Mechanism of the Diels–Alder reaction: reactions of butadiene with ethylene and cyanoethylenes J. Am. Chem. Soc. 108 5771
- 3.
Yates P and Eaton P 1960 Acceleration of the Diels–Alder reaction by aluminum chloride J. Am. Chem. Soc. 82 4436
- 4.
Fray GI and Robinson R 1961 Catalysis of the Diels–Alder reaction J. Am. Chem. Soc. 83 249
- 5.
Houk K N and Strozier R W 1973 Lewis acid catalysis of Diels–Alder reactions J. Am. Chem. Soc. 95 4094
- 6.
Rideout DC and Breslow R 1980 Hydrophobic acceleration of Diels–Alder reactions J. Am. Chem. Soc. 102 7816
- 7.
Ruiz-Lopez M F, Assfeld X, Garcia J I, Mayoral J A and Salvatella L 1993 Solvent effects on the mechanism and selectivities of asymmetric Diels–Alder reactions J. Am. Chem. Soc. 115 8780
- 8.
Breslow R and Maitra U 1984 On the origin of product selectivity in aqueous Diels–Alder reactions Tetrahedron Lett. 25 1239
- 9.
Blokzij W, Blandamer M J and Engberts J B F N 1991 Diels–Alder reactions in aqueous solutions. Enforced hydrophobic interactions between diene and dienophile J. Am. Chem. Soc. 113 4241
- 10.
Kumar A 1994 Can internal pressure describes the effect of salt in aqueous Diels–Alder reactions? A possible explanation J. Org. Chem. 59 230
- 11.
Jørgensen K A 2000 Catalytic Asymmetric Hetero‐Diels–Alder Reactions of Carbonyl Compounds and Imines Angew. Chem. Int. Ed. 39 3558
- 12.
Schaus S E, Brånalt J and Jacobsen E N 1998 Asymmetric Hetero-Diels–Alder Reactions Catalyzed by Chiral (Salen)Chromium(III) Complexes J. Org. Chem. 63 403
- 13.
Deguin B and Vogel P 1992 Hetero-Diels–Alder addition of sulfur dioxide to 1,3-dienes. Suprafaciality, regioselectivity, and stereoselectivity J. Am. Chem. Soc. 114 9210
- 14.
Streith J and Defoin A 1994 Hetero Diels–Alder Reactions with Nitroso Dienophiles: Application to the Synthesis of Natural Product Derivatives Synth. 11 1107
- 15.
Waldmann H 1994 Asymmetric Hetero Diels–Alder Reactions Synth. 6 535
- 16.
Houk K N, Lin Y T and Brown F K 1986 Evidence for the concerted mechanism of the Diels–Alder reaction of butadiene with ethylene J. Am. Chem. Soc. 108 554
- 17.
Kagan H B and Riant O 1992 Catalytic asymmetric Diels–Alder reactions Chem. Rev. 92 1007
- 18.
Nicolaou K C, Snyder S A, Montagnon T and Vassilikogiannakis G 2002 The Diels–Alder reaction in total synthesis Angew. Chem. Int. Ed Engl. 41 1668
- 19.
Du H, Long J, Hu J, Li X and Ding K 2002 3,3‘-Br2-BINOL-Zn Complex: A Highly Efficient Catalyst for the Enantioselective Hetero-Diels−Alder Reaction Org. Lett. 42 4349
- 20.
Hara K, Akiyama R and Sawamura M 2005 Strong Counteranion Effects on the Catalytic Activity of Cationic Silicon Lewis Acids in Mukaiyama Aldol and Diels−Alder Reactions Org. Lett. 25 5621
- 21.
Fang X, Chen X and Chi YC 2011 Enantioselective Diels–Alder Reactions of Enals and Alkylidene Diketones Catalyzed by N-Heterocyclic Carbenes Org. Lett. 13 4708
- 22.
Funel J A and Abele S 2013 Industrial Applications of the Diels–Alder Reaction Angew. Chem. Int. Ed. 52 3822
- 23.
Goussé C and Gandini A 1999 Diels–Alder polymerization of difurans with bismaleimides Polym. Int. 48 723
- 24.
Gacal B, Durmaz H, Tasdelen MA, Hizal G, Tunca U, Yagci Y and Demirel A L 2006 Anthracene−Maleimide-Based Diels−Alder “Click Chemistry” as a Novel Route to Graft Copolymers Macromolecules 39 5330
- 25.
Plass T, Milles S, Koehler C, Szymański J, Mueller R, Wiessler M, Schultz C and Lemke EA 2012 Amino acids for Diels–Alder reactions in living cells Angew. Chem. Int. Ed. Engl. 51 4166
- 26.
Liu Y-L and Chuoa T-W 2013 Self-healing polymers based on thermally reversible Diels–Alder chemistry Polym. Chem. 4 2194
- 27.
Shi Z, Hau S, Luo J, Kim T D, Tucker N M, Ka J W and Jen A K Y 2007 Highly Efficient Diels–Alder Crosslinkable Electro‐Optic Dendrimers for Electric‐Field Sensors Adv. Func. Mat. 17 2557
- 28.
Sarkar S, Bekyarova E and Haddon R C 2012 Chemistry at the Dirac Point: Diels–Alder Reactivity of Graphene Acc. Chem. Res. 45 673
- 29.
Gates M and Tschudi G 1952 The synthesis of morphine J. Am. Chem. Soc. 74 1109
- 30.
Woodward R B, Sondheimer F, Taub D, Heusler K and McLamore W M 1952 The Total Synthesis of Steroids J. Am. Chem. Soc. 74 4223
- 31.
Corey E J, Guzman-Perez A and Loh T-P 1994 Demonstration of the Synthetic Power of Oxazaborolidine-Catalyzed Enantioselective Diels–Alder Reactions by Very Efficient Routes to Cassiol and Gibberellic Acid J. Am. Chem. Soc. 116 3611
- 32.
Begouin J-M and Niggemann M 2013 Based Lewis Acid Catalysts Chem. Eur. J. 19 8030
Acknowledgements
This work is generously supported by the Department of Science and Technology (DST- SERB/ ECR/2015/000363) India to SM.
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S.M. and R.K. carried out the synthesis, purification, and characterization of the synthesized molecules. S.M. directed the synthetic work and wrote the paper based upon drafts written by R.K.
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Kalepu, R., Mishra, S. Lewis acid catalyst system for Diels–Alder reaction. J Chem Sci 132, 48 (2020). https://doi.org/10.1007/s12039-020-1749-8
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Keywords
- Diels–Alder reaction
- Ca(OTf)2
- Dienophiles
- Diene