Recognition-induced control of a Diels-Alder cycloaddition

Tetrahedron

Volumn 55, Issue 37, 1999, Pages 11365-11384

  Robertson, Andrew ^a   Philp, Douglas ^a   Spencer, Neil ^a  

^a UNIVERSITY OF BIRMINGHAM   (United Kingdom)

Author keywords

Cycloaddition; Furans; Kinetics; Molecular recognition

Indexed keywords

ALKADIENE; FURAN; MALEIMIDE;

ACCELERATION; ARTICLE; CALCULATION; CHEMICAL REACTION; COMPLEX FORMATION; CONTROL SYSTEM; HYDROGEN BOND; KINETICS; MOLECULAR RECOGNITION; PRIORITY JOURNAL; STEREOCHEMISTRY;

BETULACEAE;

EID: 0033543474     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(99)00633-X     Document Type: Article

References (57)

1. For general reviews, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. Dugas, H. Bioorganic Chemistry - A Chemical Approach to Enzyme Action, Third Edition, Springer-Verlag, New York, 1996. For some efficient examples, see Hosseini, M.W.; Lehn, J.M.; Jones, K.C.; Plute, K.E.; Mertes, K.B.; Mertes, M.P. J. Am. Chem. Soc. 1989, 111, 6330; Huc, I.; Pieters, J.; Rebek Jr, J. J. Am. Chem. Soc. 1994, 116, 10296; Tecilla, P.; Jubian, V.; Hamilton, A.D. Tetrahedron 1995, 51, 435.
2. For general reviews, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. Dugas, H. Bioorganic Chemistry - A Chemical Approach to Enzyme Action, Third Edition, Springer-Verlag, New York, 1996. For some efficient examples, see Hosseini, M.W.; Lehn, J.M.; Jones, K.C.; Plute, K.E.; Mertes, K.B.; Mertes, M.P. J. Am. Chem. Soc. 1989, 111, 6330; Huc, I.; Pieters, J.; Rebek Jr, J. J. Am. Chem. Soc. 1994, 116, 10296; Tecilla, P.; Jubian, V.; Hamilton, A.D. Tetrahedron 1995, 51, 435.
3. For general reviews, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. Dugas, H. Bioorganic Chemistry - A Chemical Approach to Enzyme Action, Third Edition, Springer-Verlag, New York, 1996. For some efficient examples, see Hosseini, M.W.; Lehn, J.M.; Jones, K.C.; Plute, K.E.; Mertes, K.B.; Mertes, M.P. J. Am. Chem. Soc. 1989, 111, 6330; Huc, I.; Pieters, J.; Rebek Jr, J. J. Am. Chem. Soc. 1994, 116, 10296; Tecilla, P.; Jubian, V.; Hamilton, A.D. Tetrahedron 1995, 51, 435.
4. For general reviews, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. Dugas, H. Bioorganic Chemistry - A Chemical Approach to Enzyme Action, Third Edition, Springer-Verlag, New York, 1996. For some efficient examples, see Hosseini, M.W.; Lehn, J.M.; Jones, K.C.; Plute, K.E.; Mertes, K.B.; Mertes, M.P. J. Am. Chem. Soc. 1989, 111, 6330; Huc, I.; Pieters, J.; Rebek Jr, J. J. Am. Chem. Soc. 1994, 116, 10296; Tecilla, P.; Jubian, V.; Hamilton, A.D. Tetrahedron 1995, 51, 435.
5. For general reviews, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. Dugas, H. Bioorganic Chemistry - A Chemical Approach to Enzyme Action, Third Edition, Springer-Verlag, New York, 1996. For some efficient examples, see Hosseini, M.W.; Lehn, J.M.; Jones, K.C.; Plute, K.E.; Mertes, K.B.; Mertes, M.P. J. Am. Chem. Soc. 1989, 111, 6330; Huc, I.; Pieters, J.; Rebek Jr, J. J. Am. Chem. Soc. 1994, 116, 10296; Tecilla, P.; Jubian, V.; Hamilton, A.D. Tetrahedron 1995, 51, 435.
6. Page, M.I.; Jencks, W.P. Proc. Nat. Acad. Sci. USA 1971, 68, 1678. Page, M.I. Chem. Soc. Rev. 1973, 2, 295. Kirby, A.J. Adv. Phys. Org. Chem. 1980, 17, 183. Page, M.I. in The Chemistry of Enzyme Action, Page, M.I. (Ed.), Elsevier, Amsterdam, 1984, p. 1. Menger, F.M. Acc. Chem. Res. 1985, 18,128. Page, M.I. Phil. Trans. R. Soc. Lond. B 1991, 332, 149. Kirby, A.J. Phil. Trans. R. Soc. Lond. A 1993, 345, 67. Menger, F.M. Acc. Chem. Res. 1993, 26, 206.
7. Page, M.I.; Jencks, W.P. Proc. Nat. Acad. Sci. USA 1971, 68, 1678. Page, M.I. Chem. Soc. Rev. 1973, 2, 295. Kirby, A.J. Adv. Phys. Org. Chem. 1980, 17, 183. Page, M.I. in The Chemistry of Enzyme Action, Page, M.I. (Ed.), Elsevier, Amsterdam, 1984, p. 1. Menger, F.M. Acc. Chem. Res. 1985, 18,128. Page, M.I. Phil. Trans. R. Soc. Lond. B 1991, 332, 149. Kirby, A.J. Phil. Trans. R. Soc. Lond. A 1993, 345, 67. Menger, F.M. Acc. Chem. Res. 1993, 26, 206.
8. Page, M.I.; Jencks, W.P. Proc. Nat. Acad. Sci. USA 1971, 68, 1678. Page, M.I. Chem. Soc. Rev. 1973, 2, 295. Kirby, A.J. Adv. Phys. Org. Chem. 1980, 17, 183. Page, M.I. in The Chemistry of Enzyme Action, Page, M.I. (Ed.), Elsevier, Amsterdam, 1984, p. 1. Menger, F.M. Acc. Chem. Res. 1985, 18,128. Page, M.I. Phil. Trans. R. Soc. Lond. B 1991, 332, 149. Kirby, A.J. Phil. Trans. R. Soc. Lond. A 1993, 345, 67. Menger, F.M. Acc. Chem. Res. 1993, 26, 206.
9. Page, M.I.; Jencks, W.P. Proc. Nat. Acad. Sci. USA 1971, 68, 1678. Page, M.I. Chem. Soc. Rev. 1973, 2, 295. Kirby, A.J. Adv. Phys. Org. Chem. 1980, 17, 183. Page, M.I. in The Chemistry of Enzyme Action, Page, M.I. (Ed.), Elsevier, Amsterdam, 1984, p. 1. Menger, F.M. Acc. Chem. Res. 1985, 18,128. Page, M.I. Phil. Trans. R. Soc. Lond. B 1991, 332, 149. Kirby, A.J. Phil. Trans. R. Soc. Lond. A 1993, 345, 67. Menger, F.M. Acc. Chem. Res. 1993, 26, 206.
10. Page, M.I.; Jencks, W.P. Proc. Nat. Acad. Sci. USA 1971, 68, 1678. Page, M.I. Chem. Soc. Rev. 1973, 2, 295. Kirby, A.J. Adv. Phys. Org. Chem. 1980, 17, 183. Page, M.I. in The Chemistry of Enzyme Action, Page, M.I. (Ed.), Elsevier, Amsterdam, 1984, p. 1. Menger, F.M. Acc. Chem. Res. 1985, 18,128. Page, M.I. Phil. Trans. R. Soc. Lond. B 1991, 332, 149. Kirby, A.J. Phil. Trans. R. Soc. Lond. A 1993, 345, 67. Menger, F.M. Acc. Chem. Res. 1993, 26, 206.
11. Page, M.I.; Jencks, W.P. Proc. Nat. Acad. Sci. USA 1971, 68, 1678. Page, M.I. Chem. Soc. Rev. 1973, 2, 295. Kirby, A.J. Adv. Phys. Org. Chem. 1980, 17, 183. Page, M.I. in The Chemistry of Enzyme Action, Page, M.I. (Ed.), Elsevier, Amsterdam, 1984, p. 1. Menger, F.M. Acc. Chem. Res. 1985, 18,128. Page, M.I. Phil. Trans. R. Soc. Lond. B 1991, 332, 149. Kirby, A.J. Phil. Trans. R. Soc. Lond. A 1993, 345, 67. Menger, F.M. Acc. Chem. Res. 1993, 26, 206.
12. Page, M.I.; Jencks, W.P. Proc. Nat. Acad. Sci. USA 1971, 68, 1678. Page, M.I. Chem. Soc. Rev. 1973, 2, 295. Kirby, A.J. Adv. Phys. Org. Chem. 1980, 17, 183. Page, M.I. in The Chemistry of Enzyme Action, Page, M.I. (Ed.), Elsevier, Amsterdam, 1984, p. 1. Menger, F.M. Acc. Chem. Res. 1985, 18,128. Page, M.I. Phil. Trans. R. Soc. Lond. B 1991, 332, 149. Kirby, A.J. Phil. Trans. R. Soc. Lond. A 1993, 345, 67. Menger, F.M. Acc. Chem. Res. 1993, 26, 206.
13. Page, M.I.; Jencks, W.P. Proc. Nat. Acad. Sci. USA 1971, 68, 1678. Page, M.I. Chem. Soc. Rev. 1973, 2, 295. Kirby, A.J. Adv. Phys. Org. Chem. 1980, 17, 183. Page, M.I. in The Chemistry of Enzyme Action, Page, M.I. (Ed.), Elsevier, Amsterdam, 1984, p. 1. Menger, F.M. Acc. Chem. Res. 1985, 18,128. Page, M.I. Phil. Trans. R. Soc. Lond. B 1991, 332, 149. Kirby, A.J. Phil. Trans. R. Soc. Lond. A 1993, 345, 67. Menger, F.M. Acc. Chem. Res. 1993, 26, 206.
14. For general examples, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. For other examples of accelerated cycloaddition reactions Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 7389. Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 3650. Marty, M.; Clyde-Watson, Z.; Twyman, L.J.; Nakash, M.; Sanders, J.K.M. Chem. Commun. 1998, 2265. Hamilton, A.D.; Hirst, S.C. J. Am. Chem. Soc. 1991, 113, 382. Kelly, T.R.; Ekkundi, V.S.; Meghani, P. Tetrahedron Lett. 1990, 31, 3381. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Adhya, M. J. Org. Chem. 1989, 54, 5302. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Manimaran, T.L. J. Org. Chem. 1983, 48, 3619.
15. For general examples, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. For other examples of accelerated cycloaddition reactions Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 7389. Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 3650. Marty, M.; Clyde-Watson, Z.; Twyman, L.J.; Nakash, M.; Sanders, J.K.M. Chem. Commun. 1998, 2265. Hamilton, A.D.; Hirst, S.C. J. Am. Chem. Soc. 1991, 113, 382. Kelly, T.R.; Ekkundi, V.S.; Meghani, P. Tetrahedron Lett. 1990, 31, 3381. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Adhya, M. J. Org. Chem. 1989, 54, 5302. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Manimaran, T.L. J. Org. Chem. 1983, 48, 3619.
16. For general examples, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. For other examples of accelerated cycloaddition reactions Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 7389. Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 3650. Marty, M.; Clyde-Watson, Z.; Twyman, L.J.; Nakash, M.; Sanders, J.K.M. Chem. Commun. 1998, 2265. Hamilton, A.D.; Hirst, S.C. J. Am. Chem. Soc. 1991, 113, 382. Kelly, T.R.; Ekkundi, V.S.; Meghani, P. Tetrahedron Lett. 1990, 31, 3381. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Adhya, M. J. Org. Chem. 1989, 54, 5302. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Manimaran, T.L. J. Org. Chem. 1983, 48, 3619.
17. For general examples, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. For other examples of accelerated cycloaddition reactions Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 7389. Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 3650. Marty, M.; Clyde-Watson, Z.; Twyman, L.J.; Nakash, M.; Sanders, J.K.M. Chem. Commun. 1998, 2265. Hamilton, A.D.; Hirst, S.C. J. Am. Chem. Soc. 1991, 113, 382. Kelly, T.R.; Ekkundi, V.S.; Meghani, P. Tetrahedron Lett. 1990, 31, 3381. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Adhya, M. J. Org. Chem. 1989, 54, 5302. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Manimaran, T.L. J. Org. Chem. 1983, 48, 3619.
18. For general examples, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. For other examples of accelerated cycloaddition reactions Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 7389. Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 3650. Marty, M.; Clyde-Watson, Z.; Twyman, L.J.; Nakash, M.; Sanders, J.K.M. Chem. Commun. 1998, 2265. Hamilton, A.D.; Hirst, S.C. J. Am. Chem. Soc. 1991, 113, 382. Kelly, T.R.; Ekkundi, V.S.; Meghani, P. Tetrahedron Lett. 1990, 31, 3381. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Adhya, M. J. Org. Chem. 1989, 54, 5302. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Manimaran, T.L. J. Org. Chem. 1983, 48, 3619.
19. For general examples, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. For other examples of accelerated cycloaddition reactions Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 7389. Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 3650. Marty, M.; Clyde-Watson, Z.; Twyman, L.J.; Nakash, M.; Sanders, J.K.M. Chem. Commun. 1998, 2265. Hamilton, A.D.; Hirst, S.C. J. Am. Chem. Soc. 1991, 113, 382. Kelly, T.R.; Ekkundi, V.S.; Meghani, P. Tetrahedron Lett. 1990, 31, 3381. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Adhya, M. J. Org. Chem. 1989, 54, 5302. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Manimaran, T.L. J. Org. Chem. 1983, 48, 3619.
20. For general examples, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. For other examples of accelerated cycloaddition reactions Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 7389. Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 3650. Marty, M.; Clyde-Watson, Z.; Twyman, L.J.; Nakash, M.; Sanders, J.K.M. Chem. Commun. 1998, 2265. Hamilton, A.D.; Hirst, S.C. J. Am. Chem. Soc. 1991, 113, 382. Kelly, T.R.; Ekkundi, V.S.; Meghani, P. Tetrahedron Lett. 1990, 31, 3381. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Adhya, M. J. Org. Chem. 1989, 54, 5302. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Manimaran, T.L. J. Org. Chem. 1983, 48, 3619.
21. For general examples, see Kirby, A.J. Angew. Chem. Int. Ed. Engl. 1996, 35, 707. For other examples of accelerated cycloaddition reactions Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 7389. Kang, J.; Hilmersson, G.; Santamaria, J.; Rebek Jr., J. J. Am. Chem. Soc. 1998, 120, 3650. Marty, M.; Clyde-Watson, Z.; Twyman, L.J.; Nakash, M.; Sanders, J.K.M. Chem. Commun. 1998, 2265. Hamilton, A.D.; Hirst, S.C. J. Am. Chem. Soc. 1991, 113, 382. Kelly, T.R.; Ekkundi, V.S.; Meghani, P. Tetrahedron Lett. 1990, 31, 3381. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Adhya, M. J. Org. Chem. 1989, 54, 5302. Mock, W.L.; Irra, T.A.; Wepsiec, J.P.; Manimaran, T.L. J. Org. Chem. 1983, 48, 3619.
22. In order to distinguish between transition state effects and ground state effects, we will use the description accelerated when the rate of a reaction is enhanced by the lowering of the energy of the transition state by a recognition event and the description facilitated when the extent of reaction is enhanced by the lowering of the energy of the product by a recognition event.
23. For preliminary communications on recognition-mediated acceleration and control of cycloaddition reactions, see Philp, D.; Robertson, A. Chem. Commun. 1998, 879. Booth, C.A.; Philp, D. Tetrahedron Lett. 1998, 39, 6987.
24. For preliminary communications on recognition-mediated acceleration and control of cycloaddition reactions, see Philp, D.; Robertson, A. Chem. Commun. 1998, 879. Booth, C.A.; Philp, D. Tetrahedron Lett. 1998, 39, 6987.
25. For a review of the use of furan Diels-Alder chemistry in synthesis, see Kappe, C.O.; Murphree, S.S.; Padwa, A. Tetrahedron 1997, 53, 14179. For reviews of intramolecular Diels-Alder reactions, see Brieger, G.; Bennett, J.N. Chem. Rev. 1980, 80, 63. Fallis, A.G. Can. J. Chem. 1984, 62, 183. Ciganek, E. Org. React. 1984, 32, 1. Craig, D. Chem. Soc. Rev. 1987, 16, 187. Fallis, A.G. Acc. Chem. Res. In press. For some recent examples of intramolecular Diels-Alder reactions, see Carreno, M.C.; Ruano, J.L.G.; Urbano, A. J. Org. Chem. 1996, 61, 6136. Millan, D.S.; Pham, T.T.; Lavers, J.A.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 795. Lilly, M.J.; Sherburn, M.S. Chem. Commun. 1997, 967. Wong, T.; Wilson, P.D.; Woo, S.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 7045. Bush, E.J.; Jones, D.W. J. Chem. Soc., Perkin Trans. 1 1997, 3531.
26. For a review of the use of furan Diels-Alder chemistry in synthesis, see Kappe, C.O.; Murphree, S.S.; Padwa, A. Tetrahedron 1997, 53, 14179. For reviews of intramolecular Diels-Alder reactions, see Brieger, G.; Bennett, J.N. Chem. Rev. 1980, 80, 63. Fallis, A.G. Can. J. Chem. 1984, 62, 183. Ciganek, E. Org. React. 1984, 32, 1. Craig, D. Chem. Soc. Rev. 1987, 16, 187. Fallis, A.G. Acc. Chem. Res. In press. For some recent examples of intramolecular Diels-Alder reactions, see Carreno, M.C.; Ruano, J.L.G.; Urbano, A. J. Org. Chem. 1996, 61, 6136. Millan, D.S.; Pham, T.T.; Lavers, J.A.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 795. Lilly, M.J.; Sherburn, M.S. Chem. Commun. 1997, 967. Wong, T.; Wilson, P.D.; Woo, S.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 7045. Bush, E.J.; Jones, D.W. J. Chem. Soc., Perkin Trans. 1 1997, 3531.
27. For a review of the use of furan Diels-Alder chemistry in synthesis, see Kappe, C.O.; Murphree, S.S.; Padwa, A. Tetrahedron 1997, 53, 14179. For reviews of intramolecular Diels-Alder reactions, see Brieger, G.; Bennett, J.N. Chem. Rev. 1980, 80, 63. Fallis, A.G. Can. J. Chem. 1984, 62, 183. Ciganek, E. Org. React. 1984, 32, 1. Craig, D. Chem. Soc. Rev. 1987, 16, 187. Fallis, A.G. Acc. Chem. Res. In press. For some recent examples of intramolecular Diels-Alder reactions, see Carreno, M.C.; Ruano, J.L.G.; Urbano, A. J. Org. Chem. 1996, 61, 6136. Millan, D.S.; Pham, T.T.; Lavers, J.A.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 795. Lilly, M.J.; Sherburn, M.S. Chem. Commun. 1997, 967. Wong, T.; Wilson, P.D.; Woo, S.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 7045. Bush, E.J.; Jones, D.W. J. Chem. Soc., Perkin Trans. 1 1997, 3531.
28. For a review of the use of furan Diels-Alder chemistry in synthesis, see Kappe, C.O.; Murphree, S.S.; Padwa, A. Tetrahedron 1997, 53, 14179. For reviews of intramolecular Diels-Alder reactions, see Brieger, G.; Bennett, J.N. Chem. Rev. 1980, 80, 63. Fallis, A.G. Can. J. Chem. 1984, 62, 183. Ciganek, E. Org. React. 1984, 32, 1. Craig, D. Chem. Soc. Rev. 1987, 16, 187. Fallis, A.G. Acc. Chem. Res. In press. For some recent examples of intramolecular Diels-Alder reactions, see Carreno, M.C.; Ruano, J.L.G.; Urbano, A. J. Org. Chem. 1996, 61, 6136. Millan, D.S.; Pham, T.T.; Lavers, J.A.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 795. Lilly, M.J.; Sherburn, M.S. Chem. Commun. 1997, 967. Wong, T.; Wilson, P.D.; Woo, S.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 7045. Bush, E.J.; Jones, D.W. J. Chem. Soc., Perkin Trans. 1 1997, 3531.
29. For a review of the use of furan Diels-Alder chemistry in synthesis, see Kappe, C.O.; Murphree, S.S.; Padwa, A. Tetrahedron 1997, 53, 14179. For reviews of intramolecular Diels-Alder reactions, see Brieger, G.; Bennett, J.N. Chem. Rev. 1980, 80, 63. Fallis, A.G. Can. J. Chem. 1984, 62, 183. Ciganek, E. Org. React. 1984, 32, 1. Craig, D. Chem. Soc. Rev. 1987, 16, 187. Fallis, A.G. Acc. Chem. Res. In press. For some recent examples of intramolecular Diels-Alder reactions, see Carreno, M.C.; Ruano, J.L.G.; Urbano, A. J. Org. Chem. 1996, 61, 6136. Millan, D.S.; Pham, T.T.; Lavers, J.A.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 795. Lilly, M.J.; Sherburn, M.S. Chem. Commun. 1997, 967. Wong, T.; Wilson, P.D.; Woo, S.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 7045. Bush, E.J.; Jones, D.W. J. Chem. Soc., Perkin Trans. 1 1997, 3531.
30. For a review of the use of furan Diels-Alder chemistry in synthesis, see Kappe, C.O.; Murphree, S.S.; Padwa, A. Tetrahedron 1997, 53, 14179. For reviews of intramolecular Diels-Alder reactions, see Brieger, G.; Bennett, J.N. Chem. Rev. 1980, 80, 63. Fallis, A.G. Can. J. Chem. 1984, 62, 183. Ciganek, E. Org. React. 1984, 32, 1. Craig, D. Chem. Soc. Rev. 1987, 16, 187. Fallis, A.G. Acc. Chem. Res. In press. For some recent examples of intramolecular Diels-Alder reactions, see Carreno, M.C.; Ruano, J.L.G.; Urbano, A. J. Org. Chem. 1996, 61, 6136. Millan, D.S.; Pham, T.T.; Lavers, J.A.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 795. Lilly, M.J.; Sherburn, M.S. Chem. Commun. 1997, 967. Wong, T.; Wilson, P.D.; Woo, S.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 7045. Bush, E.J.; Jones, D.W. J. Chem. Soc., Perkin Trans. 1 1997, 3531.
31. For a review of the use of furan Diels-Alder chemistry in synthesis, see Kappe, C.O.; Murphree, S.S.; Padwa, A. Tetrahedron 1997, 53, 14179. For reviews of intramolecular Diels-Alder reactions, see Brieger, G.; Bennett, J.N. Chem. Rev. 1980, 80, 63. Fallis, A.G. Can. J. Chem. 1984, 62, 183. Ciganek, E. Org. React. 1984, 32, 1. Craig, D. Chem. Soc. Rev. 1987, 16, 187. Fallis, A.G. Acc. Chem. Res. In press. For some recent examples of intramolecular Diels-Alder reactions, see Carreno, M.C.; Ruano, J.L.G.; Urbano, A. J. Org. Chem. 1996, 61, 6136. Millan, D.S.; Pham, T.T.; Lavers, J.A.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 795. Lilly, M.J.; Sherburn, M.S. Chem. Commun. 1997, 967. Wong, T.; Wilson, P.D.; Woo, S.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 7045. Bush, E.J.; Jones, D.W. J. Chem. Soc., Perkin Trans. 1 1997, 3531.
32. For a review of the use of furan Diels-Alder chemistry in synthesis, see Kappe, C.O.; Murphree, S.S.; Padwa, A. Tetrahedron 1997, 53, 14179. For reviews of intramolecular Diels-Alder reactions, see Brieger, G.; Bennett, J.N. Chem. Rev. 1980, 80, 63. Fallis, A.G. Can. J. Chem. 1984, 62, 183. Ciganek, E. Org. React. 1984, 32, 1. Craig, D. Chem. Soc. Rev. 1987, 16, 187. Fallis, A.G. Acc. Chem. Res. In press. For some recent examples of intramolecular Diels-Alder reactions, see Carreno, M.C.; Ruano, J.L.G.; Urbano, A. J. Org. Chem. 1996, 61, 6136. Millan, D.S.; Pham, T.T.; Lavers, J.A.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 795. Lilly, M.J.; Sherburn, M.S. Chem. Commun. 1997, 967. Wong, T.; Wilson, P.D.; Woo, S.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 7045. Bush, E.J.; Jones, D.W. J. Chem. Soc., Perkin Trans. 1 1997, 3531.
33. For a review of the use of furan Diels-Alder chemistry in synthesis, see Kappe, C.O.; Murphree, S.S.; Padwa, A. Tetrahedron 1997, 53, 14179. For reviews of intramolecular Diels-Alder reactions, see Brieger, G.; Bennett, J.N. Chem. Rev. 1980, 80, 63. Fallis, A.G. Can. J. Chem. 1984, 62, 183. Ciganek, E. Org. React. 1984, 32, 1. Craig, D. Chem. Soc. Rev. 1987, 16, 187. Fallis, A.G. Acc. Chem. Res. In press. For some recent examples of intramolecular Diels-Alder reactions, see Carreno, M.C.; Ruano, J.L.G.; Urbano, A. J. Org. Chem. 1996, 61, 6136. Millan, D.S.; Pham, T.T.; Lavers, J.A.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 795. Lilly, M.J.; Sherburn, M.S. Chem. Commun. 1997, 967. Wong, T.; Wilson, P.D.; Woo, S.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 7045. Bush, E.J.; Jones, D.W. J. Chem. Soc., Perkin Trans. 1 1997, 3531.
34. For a review of the use of furan Diels-Alder chemistry in synthesis, see Kappe, C.O.; Murphree, S.S.; Padwa, A. Tetrahedron 1997, 53, 14179. For reviews of intramolecular Diels-Alder reactions, see Brieger, G.; Bennett, J.N. Chem. Rev. 1980, 80, 63. Fallis, A.G. Can. J. Chem. 1984, 62, 183. Ciganek, E. Org. React. 1984, 32, 1. Craig, D. Chem. Soc. Rev. 1987, 16, 187. Fallis, A.G. Acc. Chem. Res. In press. For some recent examples of intramolecular Diels-Alder reactions, see Carreno, M.C.; Ruano, J.L.G.; Urbano, A. J. Org. Chem. 1996, 61, 6136. Millan, D.S.; Pham, T.T.; Lavers, J.A.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 795. Lilly, M.J.; Sherburn, M.S. Chem. Commun. 1997, 967. Wong, T.; Wilson, P.D.; Woo, S.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 7045. Bush, E.J.; Jones, D.W. J. Chem. Soc., Perkin Trans. 1 1997, 3531.
35. For a review of the use of furan Diels-Alder chemistry in synthesis, see Kappe, C.O.; Murphree, S.S.; Padwa, A. Tetrahedron 1997, 53, 14179. For reviews of intramolecular Diels-Alder reactions, see Brieger, G.; Bennett, J.N. Chem. Rev. 1980, 80, 63. Fallis, A.G. Can. J. Chem. 1984, 62, 183. Ciganek, E. Org. React. 1984, 32, 1. Craig, D. Chem. Soc. Rev. 1987, 16, 187. Fallis, A.G. Acc. Chem. Res. In press. For some recent examples of intramolecular Diels-Alder reactions, see Carreno, M.C.; Ruano, J.L.G.; Urbano, A. J. Org. Chem. 1996, 61, 6136. Millan, D.S.; Pham, T.T.; Lavers, J.A.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 795. Lilly, M.J.; Sherburn, M.S. Chem. Commun. 1997, 967. Wong, T.; Wilson, P.D.; Woo, S.; Fallis, A.G. Tetrahedron Lett. 1997, 38, 7045. Bush, E.J.; Jones, D.W. J. Chem. Soc., Perkin Trans. 1 1997, 3531.
36. Stereoselective Diels-Alder reactions can be performed in the presence of chiral Lewis Acids. For some recent examples, see Bruin, M.E.; Kundig, E.P. Chem. Commun. 1998, 2635. Bromidge, S.; Wilson, P.C.; Whiting, A. Tetrahedron Lett. 1998, 39, 8905. Ishihara, K.; Kurihara, H.; Matsumoto, M.; Yamamoto, H. J. Am. Chem. Soc. 1998, 120, 6920. Hubbard, R.D.; Miller, B.L. J. Org. Chem. 1998, 63, 4143. Bienamye, H. Angew. Chem. Int. Ed. Engl. 1997, 36, 2670.
37. Stereoselective Diels-Alder reactions can be performed in the presence of chiral Lewis Acids. For some recent examples, see Bruin, M.E.; Kundig, E.P. Chem. Commun. 1998, 2635. Bromidge, S.; Wilson, P.C.; Whiting, A. Tetrahedron Lett. 1998, 39, 8905. Ishihara, K.; Kurihara, H.; Matsumoto, M.; Yamamoto, H. J. Am. Chem. Soc. 1998, 120, 6920. Hubbard, R.D.; Miller, B.L. J. Org. Chem. 1998, 63, 4143. Bienamye, H. Angew. Chem. Int. Ed. Engl. 1997, 36, 2670.
38. Stereoselective Diels-Alder reactions can be performed in the presence of chiral Lewis Acids. For some recent examples, see Bruin, M.E.; Kundig, E.P. Chem. Commun. 1998, 2635. Bromidge, S.; Wilson, P.C.; Whiting, A. Tetrahedron Lett. 1998, 39, 8905. Ishihara, K.; Kurihara, H.; Matsumoto, M.; Yamamoto, H. J. Am. Chem. Soc. 1998, 120, 6920. Hubbard, R.D.; Miller, B.L. J. Org. Chem. 1998, 63, 4143. Bienamye, H. Angew. Chem. Int. Ed. Engl. 1997, 36, 2670.
39. Stereoselective Diels-Alder reactions can be performed in the presence of chiral Lewis Acids. For some recent examples, see Bruin, M.E.; Kundig, E.P. Chem. Commun. 1998, 2635. Bromidge, S.; Wilson, P.C.; Whiting, A. Tetrahedron Lett. 1998, 39, 8905. Ishihara, K.; Kurihara, H.; Matsumoto, M.; Yamamoto, H. J. Am. Chem. Soc. 1998, 120, 6920. Hubbard, R.D.; Miller, B.L. J. Org. Chem. 1998, 63, 4143. Bienamye, H. Angew. Chem. Int. Ed. Engl. 1997, 36, 2670.
40. Stereoselective Diels-Alder reactions can be performed in the presence of chiral Lewis Acids. For some recent examples, see Bruin, M.E.; Kundig, E.P. Chem. Commun. 1998, 2635. Bromidge, S.; Wilson, P.C.; Whiting, A. Tetrahedron Lett. 1998, 39, 8905. Ishihara, K.; Kurihara, H.; Matsumoto, M.; Yamamoto, H. J. Am. Chem. Soc. 1998, 120, 6920. Hubbard, R.D.; Miller, B.L. J. Org. Chem. 1998, 63, 4143. Bienamye, H. Angew. Chem. Int. Ed. Engl. 1997, 36, 2670.
41. For a catalytic method of accelerating the rate of an intramolecular Diels-Alder reaction based on hydrogen bonding, see Hirst, S.C.; Hamilton, A.D. J. Am. Chem. Soc. 1991, 113, 382. For a catalytic method of accelerating the rate of an intermolecular Diels-Alder reaction, see Walter, C.J.; Sanders, J.K.M. Angew. Chem. Int. Ed. Engl. 1995, 34, 217. In the present context, we are not concerned with catalysis, but rather ensuring that, by encoding the appropriate recognition features within the reagents, the Diels-Alder reaction is accelerated and its stereochemical outcome controlled.
42. For a catalytic method of accelerating the rate of an intramolecular Diels-Alder reaction based on hydrogen bonding, see Hirst, S.C.; Hamilton, A.D. J. Am. Chem. Soc. 1991, 113, 382. For a catalytic method of accelerating the rate of an intermolecular Diels-Alder reaction, see Walter, C.J.; Sanders, J.K.M. Angew. Chem. Int. Ed. Engl. 1995, 34, 217. In the present context, we are not concerned with catalysis, but rather ensuring that, by encoding the appropriate recognition features within the reagents, the Diels-Alder reaction is accelerated and its stereochemical outcome controlled.
43. Boissonnas, R.A.; Guttmann, S.; Huguenin, R.L.; Jaquenold, P.A.; Sandrin, E. Helv. Chim. Acta 1958, 41, 1867.
44. HH to a proton in the endo position. In other words, one might expect the exo cycloadduct to display little or no coupling between the bridgehead proton and the endo protons in the oxabicyclo[2.2.1]heptene skeleton, and, conversely, one might expect the endo cycloadduct to display a large three bond between the bridgehead proton and the exo protons in the oxabicyclo[2.2.1]heptene skeleton. In the case of 5, the 1.5 Hz coupling observed in the resonance at δ 5.18 could be assigned by COSY experiements to coupling between the bridgehead proton and one of the alkene protons of the oxabicyclo[2.2.1]heptene skeleton. This observation implies that the sample contains a cycloadduct with exo stereochemistry. This tentative assignment was confirmed by gradient nOe experiments which demonstrated a pattern of nOes which were consistent only with exo stereochemistry. The assignments of stereochemistry to the cycloadducts 4, 11 and 12 were performed by analogy with the assignment for 5 described above.
45. 8.
46. 3.
47. 3 at 30°C from initial concentrations of the reactants of 40 mM, the observed rate of reaction was approximately equal to that of the control reaction between 2 and 10. This observation is entirely consistent with the calculated value for the kinetic EM of around 40 mM.
48. Molecular mechanics calculations suggest that the source of this reversal of stereoselectivity is an intramolecular hydrogen bon between the carboxylic acid and one of the carbonyl oxygen atom of the imide in the endo cycloadduct.
49. An amide NH proton typically exhibits a downfield chemical shift change of between 2 and 3 ppm when participating in a hydrogen bond with a carbonyl oxygen atom. In this case, it is important to note that exo-5 can participate in intermolecular hydrogen bonding, and so we would expect a downfield shift of its amide NH resonance to be observed. This chemical shift change will tend to reduce the observed difference in chemical shifts between the amide NH resonances of exo-5 and endo-5, which can form an intramolecular hydrogen bond. Hence, the observed chemical shift difference between the amide NH resonances of endo-5 and exo-5 of >1.4 ppm is highly significant
50. Armarego, W.L.F.; Perrin, D.D. Purification of Laboratory Chemicals, Fourth Edition, Butterworth Heinemann, Oxford, 1997.
51. SimFit, A Program for the Analysis of Kinetic Data, Version 1.0, von Kiedrowski, G., 1994.
52. Wilcox, C.S., in Frontiers in Supramolecular Organic Chemistry and Photochemistry, Schneider, H.J.; Dürr, H. (Eds), VCH, Weinheim, 1991, p. 123.
53. Fitting of the 1:1 binding isotherm to the experimental data was accomplished using a set of custom-designed spreadsheets developed for Excel 97/98. Copies of these spreadsheets, which require the Solver add-in for Excel, are available on request from the author.
54. Mohamadi, F.; Richards, N.G.J.; Guida, W.C.; Liskamp, R.; Lipton, M.; Caufield, C.; Chang, G. Hendrickson, T.; Still, W.C. J. Comput. Chem. 1990, 11, 440.
55. Still, W.C.; Tempczyk, A.; Hawley, R.C.; Hendrickson, T. J. Am. Chem. Soc. 1990, 112, 6127.
56. Arena, G.; Cali, R.; Maccarone, E.; Passerini, A. J. Chem. Soc., Perkin Trans. 2 1993, 1941.
57. Hearn, D.; Ward, K. Aust. J. Chem. 1977, 30, 203.