Catalysis of aldehyde imination by hydrogen bonding with a simple organic disulfonamide receptor

Abstract

The disulfonamide receptor 1 catalyzes imine formation from aldehyde and amine, apparently by binding the transition state for the rate-determining nucleophilic attack of amine on the aldehyde.

References

1. (a) A. D. Hamilton, Frontiers in Bioorganic Chemistry, H. Dugas ed., Springer, Berlin, 1991, vol. 2. p. 117; (b) D. A. Bell and E. V. Anslyn, Hydrogen-Bonding Receptors: Open-Chain Catalytic Systems, in Comprehensive Supramolecular Chemistry, ed. F. Vögtle, Pergamon, New York, 1996, vol. 2 ch. 14 pp. 439–475; (c) M. C. Feiters, Supramolecular Catalysis, ed. D. N. Reinhoudt, Pergamon, New York, 1996, vol. 10, ch. 11, pp. 267–360; (d) R. Breslow, Acc. Chem. Res., 1995, 28, 146; (e) A. J. Kirby, Angew. Chem., Int. Ed. Engl., 1996, 35, 707; (f) Y. Murakami, J. Kikuchi, Y. Hisaeda and O. Hayashida, Chem. Rev., 1996, 96, 721.
2. B. Zhang and R. Breslow, J. Am. Chem. Soc., 1997, 119, 1676; M. W. Hosseini, J.-M. Lehn, K. C. Jones, K. E. Plute, K. Bowman-Mertes and M. P. Mertes, J. Am. Chem. Soc., 1989, 111, 6330; H. Fenniri, C. Dellaire, D. P. Funeriu and J.-M. Lehn, J. Chem. Soc., Perkin Trans. 2, 1997, 2073.
3. B. Dietrich, P. Viout and J.-M. Lehn, Macrocyclic Compounds Chemistry. Aspects of Organic and Inorganic Supramolecular Chemistry, VCH, Weinheim, 1992; F. Vögtle and E. Weber, Host Guest Complex Chemistry, Macrocycles: Synthesis, Structure, Applications, Springer, Berlin, 1985.
4. (a) K. Kavallieratos, S. R. de Gala, D. J. Austin and R. H. Crabtree, J. Am. Chem. Soc., 1997, 119, 2325; (b) K. Kavallieratos, C. M. Bertao and R. H. Crabtree, J. Org. Chem., 1999, 64, 1675.
5. (a) E. Fan, C. Vicent and A. D. Hamilton, New J. Chem., 1997, 21, 81; (b) J. Rebek, Jr., B. Askew, P. Ballester and A. Costero, J. Am. Chem. Soc., 1988, 110, 923; (c) J. Rebek, Jr., B. Askew, D. Killoran, D. Nemeth and F.-T. Lin, J. Am. Chem. Soc., 1987, 109, 2426; (d) P. Tecilla, S.-K. Chang and A. D. Hamilton, J. Am. Chem. Soc., 1990, 112, 9586; (e) V. Jubian, R. P. Dixon and A. D. Hamilton, J. Am. Chem. Soc., 1992, 114, 1120; (f) J. Smith, K. Ariga and E. V. Anslyn, J. Am. Chem. Soc., 1993, 115, 362; (g) J. Wolfe, D. Nemeth, A. Costero and J. Rebek, Jr., J. Am. Chem. Soc., 1988, 110, 983; (h) T. Motomura, K. Inoue, K. Kobayashi and Y. Aoyama, Tetrahedron Lett., 1991, 4757.
6. (a) V. van Axel-Castelli, A. Dalla Cort, L. Mandolini and D. N. Reinhoudt, J. Am. Chem. Soc., 1998, 120, 12 688; (b) G. L. Eichhorn and J. C. Bailer, J. Am. Chem. Soc., 1953, 75, 2905; (c) G. L. Eichhorn and I. M. Trachtenberg, J. Am. Chem. Soc., 1954, 76, 1954; (d) A. R. Boate and D. R. Eaton, Inorg. Chim. Acta, 1982, 61, 25; (e) A. R. Boate and D. R. Eaton, Can. J. Chem., 1976, 54, 3895; (f) A. R. Boate and D. R. Eaton, Can. J. Chem., 1977, 55, 2432.
7. E. S. Gould, Mechanism and Structure in Organic Chemistry, Holt, Reinhart and Winston, N.Y., 1959, p. 543.
8. With excess amine, observing the disappearance of the p-Me and CHO resonances of the aldehyde and the appearance of the p-Me and CH₂ resonances of the imine. In a typical experiment, a 5 mm NMR tube containing p-tolualdehyde (0.025 ml, 0.21 mmol) and anhydrous MgSO₄(5.2 mg, 0.043 mmol) in 0.750 ml of CD₂Cl₂ was introduced into the probe and left at –20 °C to equilibrate. Receptor 1(6.3 mg, 0.016 mmol) was added and the spectrum recorded, then BnNH₂(0.250 ml, 2.3 mmol) was added and the aldehyde resonances (δ9.94, 2.45) and the imine resonances (δ 4.80, 2.41) were monitored. Plotting the integration values vs. time for the first 20 min and linear fitting of the straight line gave the initial rates.
9. F. A. Cotton and P. F. Stokely, J. Am. Chem. Soc., 1970, 92, 294; G. Dauphin and A. Kergomard, Bull. Soc. Chim. Fr., 1961, 3, 486.
10. S. J. Benkovic, A. D. Napper and R. A. Lerner, Proc. Natl. Acad. Sci. U.S.A., 1988, 85, 5355.