Metal ion promoted transesterifications of carboxylate esters. A structure/activity study of the efficacy of Zn2+ and La3+ to catalyze the methanolysis of some aryl and aliphatic esters

Organic and Biomolecular Chemistry

Volumn 3, Issue 1, 2005, Pages 65-72

  Neverov, Alexei A ^a   Sunderland, N E ^a   Brown, R Stan ^a  

^a QUEEN S UNIVERSITY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CHEMICAL ACTIVATION; CHEMICAL BONDS; DIMERIZATION; ESTERS; HYDROLYSIS; IONS; LANTHANUM; MOLECULAR STRUCTURE; RATE CONSTANTS; REACTION KINETICS; ZINC;

ALIPHATIC ESTERS; CARBOXYLATE ESTERS; METHANOSIS; TRANSESTERIFICATION;

ESTERIFICATION;

FELIS CATUS;

EID: 11844261429     PISSN: 14770520     EISSN: None     Source Type: Journal    
DOI: 10.1039/b414763d     Document Type: Article

References (59)

1. (a) J. Koskikallio, in The Chemistry of Carboxylic Acids and Esters, ed. S. Patai, John Wiley and Sons, New York, 1969, pp. 103-136;
2. (b) M. A. Ogliaruso and J. A. Wolfe, Synthesis of Carboxylic Acids, Esters and Their Derivatives, ed. S. Patai and Z. Rappoport, John Wiley and Sons, Chichester, 1991, pp. 465-476.
3. (a) J. March, Advanced Organic Chemistry: Reactions, Mechanisms and Structure, 4th edn., John Wiley and Sons, New York, 1992, pp. 397-398 and references therein;
4. (b) M. G. Stanton, C. B. Allen, R. M. Kissling, A. L. Linclon and M. R. Gagné, J. Am. Chem. Soc., 1998, 120, 5981 and references therein;
5. R. M. Kissling and M. R. Gagné, J. Org. Chem., 2001, 66, 9005.
6. (a) T. Okano, K. Miyamoto and J. Kiji, Chem. Lett., 1995, 246;
7. (b) P. Dutta, A. Sarkar and B. C. Ranu, J. Org. Chem., 1998, 63, 6027;
8. L. Baldini, C. Bracchini, R. Cacciapaglia, A. Casnati, L. Mandolini and R. Ungaro, Chem. Eur. J., 2000, 6, 1322;
9. R. Cacciapaglia, S. Di Stephano, E. Kelderman and L. Mandolini, Angew. Chem., Int. Ed., 1999, 38, 349;
10. (e) W. M. Stevels, M. J. K. Ankoné, P. J. Dijkstra and J. Feijen, Macromolecules, 1996, 29, 8296;
11. (f) N. J. Hinde and C. D. Hall, J. Chem. Soc., Perkin Trans. 2, 1998, 1249 and references therein;
12. (g) J. Otton, S. Ratton, V. A. Vasnev, G. D. Markova, K. M. Nametov, V. I. Bakhmutov, L. I. Komarova, S. V. Vinogradova and V. V. Korshak, J. Polym. Sci. Part A Polym. Chem., 1998, 26, 2199;
13. (h) R. Cacciapaglia, S. Di Stephano and L. Mandolini, J. Org. Chem., 2001, 66, 5926.
14. G. W. Parshall and S. D. Ittel, Homogeneous Catalysis. The Applications and Chemistry of Catalysis by Soluble Transition Metal Complexes, 2nd edn., Wiley-Interscience, New York, 1992, pp. 269-296.
15. (a) A. A. Neverov, T. McDonald, G. Gibson and R. S. Brown, Can. J. Chem., 2001, 79, 1704;
16. (b) A. A. Neverov, G. Gibson and R. S. Brown, Inorg. Chem., 2003, 42, 228.
17. spH is used.
18. W. Desloges, A. A. Neverov and R. S. Brown, Inorg. Chem., 2004, 43, 6752.
19. A. A. Neverov and R. S. Brown, Org. Biomol. Chem., 2004, 2, 2245.
20. R. Cacciapaglia, S. Di Stephano, F. Fahrenkrug, U. Lüning and L. Mandolini, J. Phys. Org. Chem., 2004, 17, 350.
21. (a) S. Kitagawa, M. Munakata and A. Higashie, Inorg. Chim. Acta, 1884, 84, 79;
22. (b) A. Paulovicova, U. El-Ayanan and Y. Fukuda, Inorg. Chim. Acta, 2001, 321, 56;
23. 10a,b.
24. 13 has been investigated as to its ability to catalyze the hydrolysis of aryl esters; J. Suh, S. J. Son and M. P. Suh, Inorg. Chem., 1998, 37, 4872.
25. R. A. Joshi, M. K. Gurjar, N. K. Tripathy and M. S. Chorghade, Org. Process Res. Dev., 2001, 5, 176.
26. 2O) is 8.4.
27. F. Rived, M. Rosés and E. Bosch, Anal. Chim. Acta, 1998, 374, 309.
28. (a) V. A. Palm, Tables of Rate and Equilibrium Constants of Heterocyclic Reactions, Vol. 1(1), Proizbodstvenno-Izdatelckii Kombinat Biniti, Moscow, 1975;
29. (b) V. A. Palm, Tables of Rate and Equilibrium Constants of Heterocyclic Reactions, Suppl. Vol. 1, issue 3, Tartuskii gosudarsvennii Universitet, Tartu, 1985.
30. E. Bosch, F. Rived, M. Rosés and J. Sales, J. Chem. Soc., Perkin Trans. 2, 1999, 1953.
31. J. Lu, Ph. D. Dissertation, The University of Western Ontario: London, Ontario, Canada, 1994, p. 228.
32. B. Blesniewski, Z. Przybyszewski and Z. Paulak, J. Chem. Soc., Faraday Trans. 1, 1984, 80, 1769.
33. J. F. Kirsch and W. P. Jencks, J. Am. Chem Soc., 1964, 86, 837.
34. (a) G. T T. Gibson, A. A. Neverov and R. S. Brown, Can. J. Chem., 2003, 81, 495;
35. (b) J. S. Tsang, A. A. Neverov and R. S. Brown, J. Am. Chem. Soc., 2003, 125, 7602;
36. J. S. W. Tsang, A. A. Neverov and R. S. Brown, Org. Biomol. Chem., 2004, DOI: 10.1039/b412132e;
37. 2 active form.
38. The rationale for this is presented in ref. 8 above, and references 3 and 4 of that publication.
39. (a) Z. S. Chaw, A. Fischer and D. A. R. Happer, J. Chem. Soc. (B), 1971, 1818:
40. (b) J. Kirsch, A. Clewell and A. Simon, J. Org. Chem., 1968, 33, 127;
41. A. A. Humffray and J. J. Ryan, J. Chem. Soc. (B), 1967, 468.
42. (a) J. J. Ryan and A. A. Humffray, J. Chem. Soc. (B), 1966, 842;
43. (b) T. C. Bruice and M. Mayahi, J. Am. Chem. Soc., 1960, 82, 3067;
44. J. F. Kirsch and W. P. Jencks, J. Am. Chem. Soc., 1964, 86, 837.
45. C. G. Mitton, R. L. Schowen, M. Gresser and J. Shapley, J. Am. Chem. Soc., 1969, 91, 2036.
46. We thank Professor Andrew Williams for helpful discussions on this point.
47. -OH-catalyzed hydrolysis of aryl, the Brønsted β is computed to be ∼-0.6 for aryl groups which do not contain strongly withdrawing resonators.
48. (a) W. P. Jencks and M. Gilchrist, J. Am. Chem. Soc., 1968, 90, 2622;
49. (b) D. J. Hupe and W. P. Jencks, J. Am. Chem. Soc., 1977, 99, 451;
50. J. M. Sayer and W. P. Jencks, J. Am. Chem. Soc., 1977, 99, 464;
51. M. J. Gresser and W. P. Jencks, J. Am. Chem. Soc., 1977, 99, 6963.
52. (a) S. Thea and A. Williams, Chem. Soc Rev., 1986, 15, 125;
53. (b) A. Williams, Acc. Chem. Res., 1984, 17, 425.
54. S. Ba-Saif, A. K. Luthra and A. Williams, J. Am. Chem. Soc., 1987, 109, 6362.
55. (a) R. W. Taft, Jr., J. Am. Chem. Soc., 1952, 74, 2729, 3120;
56. (b) R. W. Taft, Jr., J. Am. Chem. Soc., 1053, 75, 4231.
57. 1 partitioning constant in the metal catalyzed reactions.
58. -1 do not allow us to rule out external methoxide attack.
59. The content of the information does not necessarily reflect the position or the policy of the federal government, and no official endorsement should be inferred.