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Thermal Cycloadditions

  • Chapter
Organic Mechanisms

Abstract

We dealt with [4+2]-cycloadditions very briefly in Section 3.3.1. As you saw there, a [4+2]-cycloaddition requires two different substrates: one of these is an alkene—or an alkyne—and the other is 1,3-butadiene or a derivative thereof. The reaction product, in this context also called the cycloadduct, is a six-membered ring with one or two double bonds. Some hetero analogs of alkenes, alkynes, and 1,3-butadiene also undergo analogous [4+2]-cycloadditions. In a [2+2]-cycloaddition an alkene or an alkyne reacts with ethene or an ethene derivative to form a four-membered ring. Again, hetero analogs may be substrates in these cycloadditions; allenes and some heterocumulenes also are suitable substrates.

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References

  • W. Carruthers, “Cycloaddition Reactions in Organic Synthesis,” Pergamon, Elmsford, NY, 1990.

    Google Scholar 

  • H. McNab, “One or More C-C Bond(s) by Pericyclic Processes,” in Comprehensive Organic Functional Group Transformations (A. R. Katritzky, O. Meth-Cohn, C. W. Rees, Eds.), Vol. 1, 771, Elsevier Science, Oxford, U. K., 1995.

    Google Scholar 

15.1

  • F. Bernardi, M. Olivucci, M. A. Robb, “Predicting Forbidden and Allowed Cycloaddition Reactions: Potential Surface Topology and Its Rationalization,” Acc. Chem. Res. 1990, 23, 405.

    Article  CAS  Google Scholar 

15.2

  • K. Fukui, “The Role of Frontier Orbitals in Chemical Reactions (Nobel Lecture),” Angew. Chem. Int. Ed. Engl. 1982, 21, 801–809.

    Article  Google Scholar 

  • R. Huisgen, “Cycloadditions — Definition, Classification, and Characterization,” Angew. Chem. Int. Ed. Engl. 1968, 7, 321–328.

    Article  CAS  Google Scholar 

  • K. N. Houk, J. Gonzalez, Y. Li, “Pericyclic Reaction Transition States: Passions and Punctilios, 1935–1995,” Acc. Chem. Res. 1995, 28, 81–90.

    Article  CAS  Google Scholar 

  • O. Wiest, K. N. Houk, “Density-Functional Theory Calculations of Pericyclic Reaction Transition Structures,” Top. Curr. Chem. 1996, 183, 1–24.

    CAS  Google Scholar 

  • K. N. Houk, Y. Li, J. D. Evanseck, “Transition Structures of Hydrocarbon Pericyclic Reactions,” Angew. Chem. Int. Ed. Engl. 1992, 31, 682–708.

    Article  Google Scholar 

15.3

  • H. L. Holmes, “The Diels-Alder Reaction: Ethylenic and Acetylenic Dienophiles,” Org. React. 1948, 4, 60–173.

    CAS  Google Scholar 

  • M. C. Kloetzel, “The Diels-Alder Reaction with Maleic Anhydride,” Org. React. 1948, 4, 1–59.

    CAS  Google Scholar 

  • L. L. Butz, A. W. Rytina, “The Diels-Alder Reaction: Quinones and Other Cyclenones,” Org. React. 1949, 5, 136–192.

    CAS  Google Scholar 

  • J. Sauer, R. Sustmann, “Mechanistic Aspects of Diels-Alder Reactions: A Critical Survey,” Angew. Chem. Int. Ed. Engl. 1980, 19, 779–807.

    Article  Google Scholar 

  • J. Jurczak, T. Bauer, C. Chapuis, “Intermolecular [4+2] Cycloadditions,” in Stereoselective Synthesis (Houben-Weyl) 4th ed., 1996, (G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann, Eds.), 1996, Vol. E21 (Workbench Edition), 5, 2735–2871, Georg Thieme Verlag, Stuttgart.

    Google Scholar 

  • F. Fringuelli, A. Taticchi, “Dienes in the Diels-Alder Reaction,” Wiley, New York, 1990.

    Google Scholar 

  • V. D. Kiselev, A. I. Konovalov, “Factors that Determine the Reactivity of Reactants in the Normal and Catalyzed Diels-Alder Reaction,” Russ. Chem. Rev. (Engl. Transl.) 1989, 58, 230.

    Article  Google Scholar 

  • W. Oppolzer, “Intermolecular Diels-Alder Reactions,” in Comprehensive Organic Synthesis (B. M. Trost, I. Fleming, Eds.), Vol. 5, 315, Pergamon Press, Oxford, U. K., 1991.

    Google Scholar 

  • F. Fringuelli, A. Taticchi, E. Wenkert, “Diels-Alder Reactions of Cycloalkenones in Organic Synthesis. A Review;” Org. Prep. Proced. Int. 1990, 22, 131–165.

    Article  CAS  Google Scholar 

  • F. Fringuelli, L. Minuti, F. Pizzo, A. Taticchi, “Reactivity and Selectivity in Lewis Acid-Catalyzed Diels-Alder Reactions of 2-Cyclohexenones,” Acta Chem. Scand. 1993, 47, 255–263.

    Article  CAS  Google Scholar 

  • E. Ciganek, “The Intramolecular Diels-Alder Reaction,” Org. React. 1984, 32, 1–374.

    CAS  Google Scholar 

  • W. R. Roush, “Stereochemical and Synthetic Studies of the Intramolecular Diels-Alder Reaction,” in Advances in Cycloaddition (D. P. Curran, Ed.) 1990, 2, Jai Press, Greenwich, CT.

    Google Scholar 

  • D. Craig, “Intramolecular [4+2] Cycloadditions,” in Stereoselective Synthesis (Houben-Weyl) 4th ed., 1996, (G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann, Eds.), 1996, Vol. E21 (Workbench Edition), 5, 2872–2952, Georg Thieme Verlag, Stuttgart.

    Google Scholar 

  • A. G. Fallis, “Harvesting Diels and Alder’s Garden: Synthetic Investigations of Intramolecular [4 + 2] Cycloadditions,” Acc. Chem. Res. 1999, 32, 464–474.

    Article  CAS  Google Scholar 

  • J. M. Coxon, R. D. J. Froese, B. Ganguly, A. P. Marchand, K. Morokuma, “On the Origins of Diastereofacial Selectivity in Diels-Alder Cycloadditions,” Synlett 1999, 1681–1703.

    Google Scholar 

  • J. I. Garcia, J. A. Mayoral, L. Salvatella, “Do Secondary Orbital Interactions Really Exist?”, Acc. Chem. Res. 2000, 33, 658–664.

    Article  CAS  Google Scholar 

15.4

  • W. E. Hanford, J. C Sauer, “Preparation of Ketenes and Ketene Dimers,” Org. React. 1946, 3, 108–140.

    Google Scholar 

  • S. Patai (Ed.), “The Chemistry of Ketenes, Allenes, and Related Compounds,” Wiley, New York, 1980.

    Google Scholar 

  • W. T. Brady, “Synthetic Applications Involving Halogenated Ketenes,” Tetrahedron 1981, 37, 2949.

    Article  CAS  Google Scholar 

  • P. W. Raynolds, “Ketene,” in Acetic Acid and Its Derivatives (V. H. Agreda, J. R. Zoeller, Eds.), 161, Marcel Dekker, New York, 1993.

    Google Scholar 

  • E. Lee-Ruff, “New Synthetic Pathways from Cyclobutanones,” in Advances in Strain in Organic Chemistry (B. Halton, Ed.) 1991, 1, Jai Press, Greenwich, CT.

    Google Scholar 

  • J. A. Hyatt, P. W. Raynolds, “Ketene Cycloadditions,” Org. React. 1994, 45, 159–646.

    CAS  Google Scholar 

15.5

  • A. Padwa (Ed.), “1,3-Dipolar Cycloaddition Chemistry,” Wiley, 1984.

    Google Scholar 

  • R. Huisgen, “Steric Course and Mechanism of 1,3-Dipolar Cycloadditions,” in Advances in Cycloaddition (D. P. Curran, Ed.) 1988, 1, 11–31, Jai Press, Greenwich, CT.

    Google Scholar 

  • R. Sustmann, “Rolf Huisgen’s Contribution to Organic Chemistry, Emphasizing 1,3-Dipolar Cycloadditions,” Heterocycles 1995, 40, 1–18.

    Article  CAS  Google Scholar 

  • A. Padwa, “Intermolecular 1,3-Dipolar Cycloadditions,” in Comprehensive Organic Synthesis (B. M. Trost, I. Fleming, Eds.), Vol. 4, 1069, Pergamon Press, Oxford, U. K., 1991.

    Google Scholar 

  • M. Cinquini, F. Cozzi, “1,3-Dipolar Cycloadditions,” in Stereoselective Synthesis (Houben-Weyl) 4th ed., 1996, (G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann, Eds.), 1996, Vol. E21 (Workbench Edition), 5, 2953–2987, Georg Thieme Verlag, Stuttgart.

    Google Scholar 

  • A. Padwa, A. M. Schoffstall, “Intramolecular 1,3-Dipolar Cycloaddition Chemistry,” in Advances in Cycloaddition (D. P. Curran, Ed.), Vol. 2, 1, JAI Press, Greenwich, CT, 1990.

    Google Scholar 

  • P. A. Wade, “Intramolecular 1,3-Dipolar Cycloadditions,” in Comprehensive Organic Synthesis (B. M. Trost, I. Fleming, Eds.), Vol. 4, 1111, Pergamon Press, Oxford, U. K., 1991.

    Google Scholar 

  • T. H. Black, “The Preparation and Reactions of Diazomethane,” Aldrichimica Acta 1983, 16, 3.

    CAS  Google Scholar 

  • V. Dave, E. W. Warnhoff, “The Reactions of Diazoacetic Esters with Alkenes, Alkynes, Heterocyclic, and Aromatic Compounds,” Org. React. 1970, 18, 217–402.

    CAS  Google Scholar 

  • K. B. G. Torsell, “Nitrile Oxides, Nitrones and Nitronates in Organic Synthesis. Novel Strategies in Synthesis,” VCH Verlagsgesellschaft, Weinheim, 1988.

    Google Scholar 

  • S. Kanemasa, O. Tsuge, “Recent Advances in Synthetic Applications of Nitrile Oxide Cycloaddition (1981–1989),” Heterocycles 1990, 30, 719–736.

    Article  CAS  Google Scholar 

  • D. P. Curran, “The Cycloaddition Approach to α-Hydroxy Carbonyls: An Emerging Alternative to the Aldol Strategy,” in Advances in Cycloaddition (D. P. Curran, Ed.) 1988, 1, 129–189, Jai Press, Greenwich, CT.

    Google Scholar 

  • R. P. Litvinovskaya, V. A. Khripach, “Regio-and Stereochemistry of 1,3-Dipolar Cycloaddition of Nitrile Oxides to Alkenes,” Russ. Chem. Rev. 2001, 70, 464–485.

    Article  Google Scholar 

  • R. L. Kuczkowski, “Formation and Structure of Ozonides,” Acc. Chem. Res. 1983, 16, 42.

    Article  CAS  Google Scholar 

  • R. L. Kuczkowski, “The Structure and Mechanism of Formation of Ozonides,” Chem. Soc. Rev. 1992, 21, 79–83.

    Article  CAS  Google Scholar 

  • O. Horie, G. K. Moortgat, “Gas-Phase Ozonolysis of Alkenes. Recent Advances in Mechanistic Investigations,” Acc. Chem. Res. 1998, 31, 387–396.

    Article  CAS  Google Scholar 

  • W. Sander, “Carbonyl Oxides: Zwitterions or Diradicals?”, Angew. Chem. Int. Ed. Engl. 1990, 29, 344–354.

    Article  Google Scholar 

  • W. H. Bunnelle, “Preparation, Properties, and Reactions of Carbonyl Oxides,” Chem. Rev. 1991, 91, 335–362.

    Article  CAS  Google Scholar 

  • K. Ishiguro, T. Nodima, Y. Sawaki, “Novel Aspects of Carbonyl Oxide Chemistry,” J. Phys. Org. Chem. 1997, 10, 787–796.

    Article  CAS  Google Scholar 

Further Reading

  • S. Danishefsky, “Cycloaddition and Cyclocondensation Reactions of Highly Functionalized Dienes: Applications to Organic Synthesis,” Chemtracts: Org. Chem. 1989, 2, 273–297.

    CAS  Google Scholar 

  • T. Kametani, S. Hibino, “The Synthesis of Natural Heterocyclic Products by Hetero Diels-Alder Cycloaddition Reactions,” Adv. Heterocycl. Chem. 1987, 42, 246.

    Google Scholar 

  • J. A. Coxon, D. Q. McDonald, P. J. Steel, “Diastereofacial Selectivity in the Diels-Alder Reaction,” in Advances in Detailed Reaction Mechanisms (J. M. Coxon, Ed.), Vol. 3, Jai Press, Greenwich, CT, 1994.

    Google Scholar 

  • J. D. Winkler, “Tandem Diels-Alder Cycloadditions in Organic Synthesis,” Chem. Rev. 1996, 96, 167–176.

    Article  CAS  Google Scholar 

  • C. O. Kappe, S. S. Murphree, A. Padwa, “Synthetic Applications of Furan Diels-Alder Chemistry,” Tetrahedron 1997, 53 14179–14231.

    Article  CAS  Google Scholar 

  • D. Craig, “Stereochemical Aspects of the Intramolecular Diels-Alder Reaction,” Chem. Soc. Rev. 1987, 16, 187.

    Article  CAS  Google Scholar 

  • G. Helmchen, R. Karge, J. Weetman, “Asymmetric Diels-Alder Reactions with Chiral Enoates as Dienophiles,” in Modern Synthetic Methods (R. Scheffold, Ed.), Vol. 4, 262, Springer, Berlin, 1986.

    Google Scholar 

  • L. F. Tietze, G. Kettschau, “Hetero Diels-Alder Reactions in Organic Chemistry,” Top. Curr. Chem. 1997, 189, 1–120.

    Article  CAS  Google Scholar 

  • K. Neuschuetz, J. Velker, R. Neier, “Tandem Reactions Combining Diels-Alder Reactions with Sigmatropic Rearrangement Processes and Their Use in Synthesis,” Synthesis 1998, 227–255.

    Google Scholar 

  • D. L. Boger, M. Patel, “Recent Applications of the Inverse Electron Demand Diels-Alder Reaction,” in Progress in Heterocyclic Chemistry (H. Suschitzky, E. F. V. Scriven, Eds.) 1989, 1, 36–67, Pergamon Press, Oxford, U. K.

    Google Scholar 

  • M. J. Tashner, “Asymmetric Diels-Alder Reactions,” in Organic Synthesis: Theory and Applications (T. Hudlicky, Ed.) 1989, 1, Jai Press, Greenwich, CT.

    Google Scholar 

  • H. B. Kagan, O. Riant, “Catalytic Asymmetric Diels-Alder Reactions,” Chem. Rev. 1992, 92, 1007.

    Article  CAS  Google Scholar 

  • T. Oh, M. Reilly, “Reagent-Controlled Asymmetric Diels-Alder Reactions,” Org. Prep. Proced. Int. 1994, 26, 129.

    Article  CAS  Google Scholar 

  • I. E. Marko, G. R. Evans, P. Seres, I. Chelle, Z. Janousek, “Catalytic, Enantioselective, Inverse Eectron-Demand Diels-Alder Reactions of 2-Pyrone Derivatives,” Pure Appl. Chem. 1996, 68, 113.

    Article  CAS  Google Scholar 

  • H. Waldmann, “Asymmetric Hetero-Diels-Alder Reactions,” Synthesis 1994, 635–651.

    Google Scholar 

  • H. Waldmann, “Asymmetric Aza-Diels-Alder Reactions,” in Organic Synthesis Highlights II (H. Waldmann, Ed.), VCH, Weinheim, New York, 1995, 37–47.

    Chapter  Google Scholar 

  • L. C. Dias, “Chiral Lewis Acid Catalysts in Diels Alder Cycloadditions: Mechanistic Aspects and Synthetic Applications of Recent Systems,” J. Braz. Chem. Soc. 1997, 8, 289–332.

    CAS  Google Scholar 

  • D. Carmona, M. Pilar Lamata, L. A. Oro, “Recent Advances in Homogeneous Enantioselective Diels-Alder Reactions Catalyzed by Chiral Transition-Metal Complexes,” Coord. Chem. Rev. 2000, 200–2, 717–772.

    Article  Google Scholar 

  • F. Fringuelli, O. Piermatti, F. Pizzo, L. Vaccaro, “Recent Advances in Lewis Acid Catalyzed Diels-Alder Reactions in Aqueous Media,” Eur. J. Org. Chem. 2001, 3, 439–455.

    Article  Google Scholar 

  • B. R. Bear, S. M. Sparks, K. J. Shea, “The Type 2 Intramolecular Diels-Alder Reaction: Synthesis and Chemistry of Bridgehead Alkenes,” Angew. Chem. Int. Ed. Engl. 2001, 40, 820–849.

    Article  CAS  Google Scholar 

  • E. J. Corey, “Catalytic Enantioselective Diels-Alder Reaction: Methods, Mechanistic Basis, Reaction Pathways, and Applications,” Angew. Chem. Int. Ed. Engl. 2002, 41, 1650–1667.

    Article  CAS  Google Scholar 

  • K. C. Nicolaou, S. A. Snyder, T. Montagnon, G. E. Vassilikogiannakis, “The Diels-Alder Reaction in Total Synthesis,” Angew. Chem. Int. Ed. Engl. 2002, 41, 1668–1698.

    Article  CAS  Google Scholar 

  • J. D. Roberts, C. M. Sharts, “Cyclobutane Derivatives from Thermal Cycloaddition Reactions”, Org. React. 1962, 12, 1–56.

    CAS  Google Scholar 

  • B. B. Snider, “Thermal [2+2] Cycloadditions,” in Stereoselective Synthesis (Houben-Weyl) 4th ed., 1996, (G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann, Eds.), 1996, Vol. E21 (Workbench Edition), 5, 3060–3084, Georg Thieme Verlag, Stuttgart.

    Google Scholar 

  • J. Mulzer, “Natural Product Synthesis via 1,3-Dipolar Cycloadditions,” in Organic Synthesis Highlights (J. Mulzer, H.-J. Altenbach, M. Braun, K. Krohn, H.-U. Reißig, Eds.), VCH, Weinheim, New York, 1991, 77–95.

    Google Scholar 

  • K. V. Gothelf, K. A. Jürgensen, “Metal-Catalyzed Asymmetric 1,3-Dipolar Cycloaddition Reactions,” Acta Chem. Scand. 1996, 50, 652.

    Article  CAS  Google Scholar 

  • P. N. Confalone, E. M. Huie, “The [3+2] Nitrone-Olefin Cycloaddition Reaction,” Org. React. 1988, 36, 1–173.

    CAS  Google Scholar 

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Editors and Affiliations

  1. Department of Chemistry, University of Missouri-Columbia, 601 S. College Avenue, Columbia, Missouri, 65211

    Michael Harmata (Norman Rabjohn Distinguished Professor of Chemistry) (Norman Rabjohn Distinguished Professor of Chemistry)

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(2010). Thermal Cycloadditions. In: Harmata, M. (eds) Organic Mechanisms. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-03651-4_15

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