Triflic acid mediated dealkylative lactonisation via NMR-observable alkyloxonium intermediates

European Journal of Organic Chemistry

Volumn , Issue 4, 2009, Pages 516-524

  Muñoz, M Paz ^a,b   Lloyd Jones, Guy C ^b  

^a INSTITUTO DE QUÍMICA ORGÁNICA GENERAL   (Spain)

^b UNIVERSITY OF BRISTOL   (United Kingdom)

Author keywords

Allylmalonates; Intermediates; Kinetics; Lactones; Triflic acid

Indexed keywords

EID: 60849117512     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.200800970     Document Type: Article

References (57)

1. a) M. F. Ansell, M. H. Palmer, Q. Rev., Chem. Soc. 1964, 211-225;
2. +: E. J. Boorman, R. P. Linstead, J. Chem. Soc. 1933, 577-580;
3. c) E. J. Boorman, R. P. Linstead, H. N. Rydon, J. Chem. Soc. 1933, 568-576;
4. d) R. P. Linstead, H. N. Rydon, J. Chem. Soc. 1933, 580-586;
5. e) R. S. Mali, K. N. Babu, Helv. Chim. Acta 2002, 85, 3525-3531;
6. f) reaction with E+: R. T. Arnold, K. L. Lindsay, J. Am. Chem. Soc. 1953, 75, 1048-1049;
7. g) J. Klein, J. Am. Chem. Soc. 1959, 81, 3611-3614;
8. h) M. Eriksson, A. Hjelmencrantz, M. Nilsson, T. Olsson, Tetrahedron 1995, 51, 12631-12644.
9. a) I. J. S. Fairlamb, S. Grant, S. Tommasi, J. M. Lynam, M. Bandini, H. Dong, Z. Lin, A. C. Whitwood, Adv. Synth. Catal. 2006, 348, 2515-2530;
10. b) F. Grau, A. Heumann, E. Duñach, Angew. Chem. Int. Ed. 2006, 45, 7285-7289.
11. a) G. Stork, A. W. Burgstahler, J. Am. Chem. Soc. 1955, 77, 5068-5077;
12. b) M. F. Ansell, M. H. Palmer, J. Chem. Soc. 1963, 2640-2644;
13. c) G. Berti, Tetrahedron 1958, 4, 393-402.
14. a) R. Verhe, N. de Kimpe, L. de Buyck, N. Schamp, Synth. Commun. 1981, 11,35-42;
15. b) J.-F. Roudier, A. Foucaud, Tetrahedron Lett. 1984, 25, 4375-4378;
16. c) S. GowriSankar, C. G. Lee, J. N. Kim, Tetrahedron Lett. 2004, 45, 6949-6953;
17. d) M. F. Oswald, A. F. Parsons, W. Yang, M. Bowden, Tetrahedron Lett. 2005, 46, 8087-8089.
18. O. Piva, Tetrahedron 1994, 50, 13687-13696.
19. a) J. Klein, J. Org. Chem. 1958, 23, 1209-1210;
20. b) other mechanisms have been proposed for these substrates: M. Tiecco, M. Tingoli, L. Testaferri, D. Bartoli, Synth. Commun. 1989, 19, 2817-2824;
21. c) M. Tiecco, L. Testaferri, M. Tingoli, D. Bartoli, Tetrahedron 1989, 45, 6819-6832;
22. d) M. Tiecco, L. Testaferri, M. Tingoli, D. Bartoli, Tetrahedron 1990, 46, 7139-7150.
23. R. T. Arnold, M. de Moura Campos, K. L. Lindsay, J. Am. Chem. Soc. 1953, 75, 1044-1047.
24. N. Fey, J.N. Harvey, G. C. Lloyd-Jones, M. P. Muñoz, P. A. Slatford, unpublished results.
25. For the triflic acid catalysed cycloisomerisation of olefinic car-boxylic acids, see: L. Coulombe, E. Duñach, Synth. Comunn. 2005, 35, 153-160.
26. 8] and triflic acid in acetic acid has been reported: M. Tiecco, L. Testaferri, M. Tingoli, Tetrahedron 1993, 49, 5351 -5358. However, the reaction of 1 with TfOH in the presence of 2 equiv. of AcOH gave the same mixture 2:1 of the lactone 2 in 69%, with no incorporation of the acetate unit.
27. W. E. Fristad, S. S. Hershberger, J. Org. Chem. 1985, 50, 1026-1031.
28. A similar intermediate has been proposed in the reaction of olefinic amides with triflic acid: C. M. Marson, A. Fallah, Tetrahedron Lett. 1994, 35, 293-296.
29. 1H NMR spectroscopy: K. B. Hong, M. G. Donahue, J. N. Johnston, J. Am. Chem. Soc. 2008, 130, 2323-2328.
30. E. S. Stoyanov, K.-C. Kim, C. A. Reed, J. Phys. Chem. A 2004, 108, 9310-9315.
31. 1H NMR spectroscopy) and regenerate TfOH.
32. The unsubstituted malonate 17 had to be pre-deuterated in the acidic position in order to achieve high incorporation of deuterium in the lactonisation, due to H/D exchange of the malonate C-H proton with the triflic acid. Lactone d-18 was obtained with H in that position due to D/H exchange during purification by column chromatography.
33. 2 4%.
34. [8]
35. Protonation of the ester can also explain the easier hydrolysis of the tert-buty1 ester to give lactone 12.
36. Both isomers were separable by column chromatography and were analysed independently to give similar results.
37. The identity of the diastereoisomers was established by NOE and theoretical calculations of the energy of the possible isomers. For an example of the use of DPFGSE-NOE experiments for the determination of the structure of γ-butyrolac-tones, see: X. Xie, S. Tschan, F. Glorius, Magn. Reson. Chem. 2007, 45, 381-388.
38. 2 36%.
39. The unsubstituted malonate 27 had to be pre-deuterated in the acidic position in order to achieve high incorporation of deuterium in the lactonisation, due to H/D exchange of the malonate C-H proton with the triflic acid. Lactone d-28 was obtained with H in that position due to D/H exchange during purification by column chromatography.
40. For mechanisms of isomerisation of santoine derivatives, see: D. H. R. Barton, J. Org. Chem. 1950, 15, 466-470.
41. A. J. Kirby, Adv. Phys. Org. Chem. 1980, 17, 183-278.
42. a) C. F. Bernasconi, S. A. Hibdon, S. E. McMurry, J. Am. Chem. Soc. 1982, 104, 3459-3471;
43. b) A. J. Kirby, N. H. Wil-liams, J. Chem. Soc. Perkin Trans. 2 1994, 643-648;
44. c) E. T. Harper, M. L. Bender, J. Am. Chem. Soc. 1965, 87, 5625-5632;
45. d) A. J. Kresge, Y. Yin, J. Phys. Org. Chem. 1988, 1, 247-257.
46. [8] suggest that the intramolecular transfer might be the preferred pathway.
47. For acid-catalysed intramolecular additions of carboxy groups to vinylsilanes, see: K. Miura, J. Hayashida, T. Takahashi, H. Nishikori, A. Hosomi, J. Organomet. Chem. 2003, 686, 242-250.
48. B. Bobranski, R. Wojtowski, Rocz. Chem. 1966, 40, 1707-1715.
49. a) E. Wagner, B. Bobranski, Pol. J. Pharmacol. Pharm. 1977, 29, 565-569;
50. b) M. Konieczny, J. Toedorczyk, E. Wagner, Arch. Immunol. Ther. Exp. 1971, 19, 915-931.
51. E. W. Maynert, E. Washburn, J. Am. Chem. Soc. 1953, 75, 700-704.
52. B. Lambrey, O. Lafont, C. Jacquot, Eur. J. Med. Chem. 1980, 15, 463-468.
53. M. Rautio, K. Vuori, Acta Chem. Scand., Ser. B: Org. Chem. Biochem. 1980, 34, 770-772.
54. Comercially available.
55. T. Kawamata, S. Inayama, K. Sata, Chem. Pharm. Bull. 1980, 28, 277-281.
56. a) L. Lamarque, M. Campredon, A. Meou, P. Brun, R. Faure, Magn. Reson. Chem. 1998, 36, 463-665;
57. b) E. Camapigne, J. C. Beckman, Synthesis 1978, 385-388.