Improved Conversion of 6-endo-Tosyloxybicyclo[2.2.2]octan-2-ones into 6-exo-Acetoxy and 6-exo-Benzoyloxybicyclo[2.2.2]octan-2-ones 1

Advanced Synthesis and Catalysis

Volumn 341, Issue 7, 1999, Pages 687-690

  Marini Bettolo, Rinaldo ^a   Migneco, Luisa Maria ^a   Moretti, Piergiorgio ^a   Scarpelli, Rita ^a  

^a SAPIENZA UNIVERSITY OF ROME   (Italy)

Author keywords

Bicyclo 2.2.2 octan 2 ones; Isomerizations; Nucleophilic displacement; Synthetic methods; Tetraalkylammoniumacetates

Indexed keywords

EID: 0347710603     PISSN: 16154150     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Article

References (59)

1. a) M. Berettoni, R. Marini Bettolo, V. Montanari, T. Prencipe, S. Romeo, Helv. Chim. Acta 1991, 74, 1671;
2. b) M. Berettoni, G. De Chiara, T. Iacoangeli, P. Lo Surdo, R. Marini Bettolo, L. Montagnini di Mirabello, L. Nicolini, R. Scarpelli, Helv. Chim. Acta 1996, 79, 2035
3. a) J. Steigman, L. P. Hammett, J. Am. Chem. Soc. 1937, 59, 2536;
4. b) A. Streitwieser Jr., T. D. Walsh, J. R. Wolfe Jr., J. Am. Chem. Soc. 1965, 87, 3682;
5. c) A. C. Cope, D. L. Nealy, J. Am. Chem. Soc. 1965, 87, 3122;
6. d) R. Baker, J. Hudec, K. L. Rabone, J. Chem. Soc. (C) 1969, 1605;
7. e) B. L. Murr, J. A. Conkling, J. Am. Chem. Soc. 1970, 92, 3462;
8. f) C. J. Kim, H. C. Brown, J. Am. Chem. Soc. 1972, 94, 5051;
9. g) D. M. Floyd, G. A. Crosby, N. M. Weinshenker, Tetrahedron Lett. 1972, 3265;
10. h) E. J. Corey, S. Terashima, Tetrahedron Lett. 1972, 111;
11. i) H. Maskill, J. Am. Chem. Soc. 1976, 98, 8482;
12. j) S. J. Cristol, R. M. Strom, J. Am. Chem. Soc. 1980, 102, 5577;
13. k) R. W. Binkley, J. Org. Chem. 1991, 56, 3892;
14. l) G. Casiraghi, P. Spanu, G. Rassu, L. Pinna, F. Ulgheri, J. Org. Chem. 1994, 59, 2906;
15. m) A. G. M. Barrett, D. C. Braddock, R. A. James, N. Koike, P. A. Procopiou, J. Org. Chem. 1998, 63, 6273
16. Later, other tetraalkylammonium carboxylates [2d-m] and tetraalkylammonium salts [4] were used to this end.
17. a) N. Afza, A. Malik, W. Voelter, Z. Naturforsch. 1984, 39b, 840;
18. b) R. W. Binkley, D. J. Koholic, J. Carbohydr. Chem. 1984, 3, 85;
19. c) G. Cainelli, F. Manescalchi, G. Martelli, M. Panunzio, L. Plessi, Tetrahedron Lett. 1985, 3369;
20. d) G. Cainelli, D. Giacomini, M. Panunzio, G. Martelli, G. Spunta, Tetrahedron 1985, 41, 1385
21. As a matter of fact, we had previously obtained 2 from ketol 1b by the Mitsunobu procedure [6] by which, however, we were unable to convert ketol 3b into 4. A similar result was later reported by Mori and Matsushima [7], whose attempts to convert the 6-endo-hydroxy-1-methylbicyclo[2.2.2]octan-2-one 7a into the corresponding 6-exo-benzoate, by the same methodology, were also unsuccessful.
22. O. Mitsunobu, Synthesis 1981, 1
23. K. Mori, Y. Matsushima, Synthesis 1993, 406
24. a) W. Herz, R.N. Mirrington, H. Young, Y.Y. Lin, J. Org. Chem. 1968, 33, 4210;
25. b) R.B. Kelly, J. Eber, H.K. Hung, Can. J. Chem. 1973, 51, 2534;
26. c) R.B. Kelly, J. Eber, H.K. Hung, J. Chem. Soc. Chem. Commun. 1973, 689;
27. d) K. Wiesner, T. Y. R. Tsai, K. Huber, S. E. Bolton, Tetrahedron Lett. 1973, 1233;
28. e) K. Wiesner, T. Y. R. Tsai, K. Huber, S. E. Bolton, R. Vlahov, J. Am. Chem. Soc. 1974, 96, 4990;
29. f) M. Przybylska, T. Y. R. Tsai, K. Wiesner, J. Chem. Soc. Chem. Comm. 1975, 297;
30. g) K. Wiesner, Chem. Soc. Rev. 1977, 6, 413;
31. h) K. S. Atwal, R. Marini Bettolo, I. H. Sanchez, T. Y. R. Tsai, K. Wiesner, Can. J. Chem. 1978, 56, 1102;
32. i) R. B. Kelly, M. L. Harley, S. J. Alward, Can. J. Chem. 1980, 58, 755;
33. j) S. P. Sethi, K. S. Atwal, R. Marini Bettolo, T. Y. R. Tsai, K. Wiesner, Can. J. Chem. 1980, 58, 1889;
34. k) E. E. van Tamelen, J. G. Carlson, R. K. Russell, S. R. Zawacky, J. Am. Chem. Soc. 1981, 103, 4615;
35. l) D. Bravetti, R. Marini Bettolo, A. Lupi, Helv. Chim. Acta 1982, 65, 371;
36. m) R. Marini Bettolo, P. Tagliatesta, A. Lupi, D. Bravetti, Helv. Chim. Acta 1983, 66, 760;
37. n) R. Marini Bettolo, P. Tagliatesta, A. Lupi, D. Bravetti, Helv. Chim. Acta 1983, 66, 1922;
38. o) R. B. Kelly, M. L. Harley, S. J. Alward, R. N. Rej, G. Gowda, A. Mukhopadhyay, P. S. Manchand, Can. J. Chem. 1983, 61, 269;
39. p) E. E. van Tamelen, S. R. Zawacky, R. K. Russell, J.G. Carlson, J. Am. Chem. Soc. 1983, 105, 142;
40. q) A. Lupi, M. Patamia, I. Grgurina, R. Marini Bettolo, O. Di Leo, P. Gioia, S. Antonaroli, Helv. Chim. Acta 1984, 67, 226
41. B. M. Trost, I. Fleming in Comprehensive Organic Chemistry, Vol. 6; Pergamon Press; Oxford 1991, pp. 18-22, and references therein.
42. B. De Santis, A. L. Iamiceli, R. Marini Bettolo, L. M. Migneco, R. Scarpelli, G. Fabrizi, G. Cerichelli, D. Lamba, Helv. Chim. Acta 1998, 81, 2375
43. This method is very often used for the preparation of bicyclo[2.2.2]octane systems. For a series of representative examples see ref. [1] in [10].
44. The conversion of syn 7-bromonorbornan-2-one and syn 7-tosyloxynorbornan-2-one into anti 7-chloronorbornan-2-one and anti 7-acetoxynorbornan-2-one, respectively, was also described [13]. Recently, to the carbonyl group in these systems a role in facilitating the displacement of the nucleofuge was ascribed [14].
45. a) J. T. Lumb, G. H. Whitham, Chem. Comm. 1966, 400;
46. b) P. G. Gassmann, J. L. Marshall, J. M. Hornback, J. Am. Chem. Soc. 1969, 91, 5811
47. J. J. Nash, T. Waugh, H. Morrison, Tetrahedron Lett. 1998, 6449
48. a) R. A. Bell, R. E. Ireland, Tetrahedron Lett. 1963, 269;
49. b) R. W. Guthrie, A. Philipp, Z. Valenta, K. Wiesner, Tetrahedron Lett. 1965, 2945;
50. c) R. W. Guthrie, Z. Valenta, K. Wiesner, Tetrahedron Lett. 1966, 4645;
51. d) R. A. Bell, R. E. Ireland, R. A. Partyka, J. Am. Chem. Soc. 1966, 31, 2530;
52. e) K. Mori, Y. Nakahara, M. Matsui, Tetrahedron 1972, 28, 3217;
53. f) K. Wiesner, T. Y. R. Tsai, K. Huber, S. Bolton, Tetrahedron Lett. 1973, 1233;
54. g) R. B. Kelly, J. Eber, H. K. Hung, Can. J. Chem. 1973, 51, 2534;
55. h) K. Mori, E. Nagano, Biocatalysis 1990, 3, 25;
56. i) A. Bartoletti, M. Berettoni, F. Catteruccia, G. De Chiara, R. Marini Bettolo, C. Mastrangeli, R. Scarpelli, C. Tozzi, D. Lamba, Gazz. Chim. Ital. 1996, 126, 223
57. From an experimental point of view, because of its handling ease, being a crystalline solid, TBAB represents the best choice.
58. An acceleration of the inversion process with TBAA, changing acetone for benzene, was already described in the course of the preparation of exo-norbornyl-2d-acetate from endo-norbornyl-2d-brosylate [2e].
59. M. Nojima, S. Hasegawa, N. Tokura, Bull. Chem. Soc. Jpn. 1973, 46, 1254