The endocyclic restriction test: Investigation of the geometries of nucleophilic substitution at phosphorus(III) and phosphorus(V)

Journal of the American Chemical Society

Volumn 118, Issue 38, 1996, Pages 9052-9061

  Tollefson, Michael B ^a   Li, James J ^a   Beak, Peter ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

PHOSPHINE DERIVATIVE; PHOSPHINIC ACID DERIVATIVE;

ARTICLE; CHIRALITY; DRUG STRUCTURE; MOLECULAR DYNAMICS;

EID: 0029848324     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961375g     Document Type: Article

References (51)

1. For examples of inversion of configuration at phosphine centers see: (a) Smith, D. J. H.; Trippett, S. J. Chem. Soc. Chem. Commun. 1969, 855. (b) Corfield, J. R.; Oram, R. K.; Smith D. J. H.; Trippett, S. J. Chem. Soc. Perkin Trans. 1, 1972, 713. (c) Kyba, E. P. J. Am. Chem. Soc. 1975, 97, 2554. (d) Kyba, E. P. J. Am. Chem. Soc. 1976, 98, 4805. (e) Omelanczuk, J.; Mikolajczyk, M. J. Chem. Soc. Chem. Commun. 1976, 1025. (f) Mikolajczyk, M.; Omelanczuk, J.; Perlikowska, W. Tetrahedron 1979, 35, 1531. (g) Mikolajczk, M. Pure Appl. Chem. 1980, 52, 959. (h) Nielsen, J.; Dahl, O. J. Chem. Soc. Perkin Trans. 2 1984, 553. (i) Dahl. O. Tetrahedron Lett. 1981, 22, 3281. (j) Dahl, O. Phosphorus and Sulfur 1983, 18, 201.
2. For examples of inversion of configuration at phosphine centers see: (a) Smith, D. J. H.; Trippett, S. J. Chem. Soc. Chem. Commun. 1969, 855. (b) Corfield, J. R.; Oram, R. K.; Smith D. J. H.; Trippett, S. J. Chem. Soc. Perkin Trans. 1, 1972, 713. (c) Kyba, E. P. J. Am. Chem. Soc. 1975, 97, 2554. (d) Kyba, E. P. J. Am. Chem. Soc. 1976, 98, 4805. (e) Omelanczuk, J.; Mikolajczyk, M. J. Chem. Soc. Chem. Commun. 1976, 1025. (f) Mikolajczyk, M.; Omelanczuk, J.; Perlikowska, W. Tetrahedron 1979, 35, 1531. (g) Mikolajczk, M. Pure Appl. Chem. 1980, 52, 959. (h) Nielsen, J.; Dahl, O. J. Chem. Soc. Perkin Trans. 2 1984, 553. (i) Dahl. O. Tetrahedron Lett. 1981, 22, 3281. (j) Dahl, O. Phosphorus and Sulfur 1983, 18, 201.
3. For examples of inversion of configuration at phosphine centers see: (a) Smith, D. J. H.; Trippett, S. J. Chem. Soc. Chem. Commun. 1969, 855. (b) Corfield, J. R.; Oram, R. K.; Smith D. J. H.; Trippett, S. J. Chem. Soc. Perkin Trans. 1, 1972, 713. (c) Kyba, E. P. J. Am. Chem. Soc. 1975, 97, 2554. (d) Kyba, E. P. J. Am. Chem. Soc. 1976, 98, 4805. (e) Omelanczuk, J.; Mikolajczyk, M. J. Chem. Soc. Chem. Commun. 1976, 1025. (f) Mikolajczyk, M.; Omelanczuk, J.; Perlikowska, W. Tetrahedron 1979, 35, 1531. (g) Mikolajczk, M. Pure Appl. Chem. 1980, 52, 959. (h) Nielsen, J.; Dahl, O. J. Chem. Soc. Perkin Trans. 2 1984, 553. (i) Dahl. O. Tetrahedron Lett. 1981, 22, 3281. (j) Dahl, O. Phosphorus and Sulfur 1983, 18, 201.
4. For examples of inversion of configuration at phosphine centers see: (a) Smith, D. J. H.; Trippett, S. J. Chem. Soc. Chem. Commun. 1969, 855. (b) Corfield, J. R.; Oram, R. K.; Smith D. J. H.; Trippett, S. J. Chem. Soc. Perkin Trans. 1, 1972, 713. (c) Kyba, E. P. J. Am. Chem. Soc. 1975, 97, 2554. (d) Kyba, E. P. J. Am. Chem. Soc. 1976, 98, 4805. (e) Omelanczuk, J.; Mikolajczyk, M. J. Chem. Soc. Chem. Commun. 1976, 1025. (f) Mikolajczyk, M.; Omelanczuk, J.; Perlikowska, W. Tetrahedron 1979, 35, 1531. (g) Mikolajczk, M. Pure Appl. Chem. 1980, 52, 959. (h) Nielsen, J.; Dahl, O. J. Chem. Soc. Perkin Trans. 2 1984, 553. (i) Dahl. O. Tetrahedron Lett. 1981, 22, 3281. (j) Dahl, O. Phosphorus and Sulfur 1983, 18, 201.
5. For examples of inversion of configuration at phosphine centers see: (a) Smith, D. J. H.; Trippett, S. J. Chem. Soc. Chem. Commun. 1969, 855. (b) Corfield, J. R.; Oram, R. K.; Smith D. J. H.; Trippett, S. J. Chem. Soc. Perkin Trans. 1, 1972, 713. (c) Kyba, E. P. J. Am. Chem. Soc. 1975, 97, 2554. (d) Kyba, E. P. J. Am. Chem. Soc. 1976, 98, 4805. (e) Omelanczuk, J.; Mikolajczyk, M. J. Chem. Soc. Chem. Commun. 1976, 1025. (f) Mikolajczyk, M.; Omelanczuk, J.; Perlikowska, W. Tetrahedron 1979, 35, 1531. (g) Mikolajczk, M. Pure Appl. Chem. 1980, 52, 959. (h) Nielsen, J.; Dahl, O. J. Chem. Soc. Perkin Trans. 2 1984, 553. (i) Dahl. O. Tetrahedron Lett. 1981, 22, 3281. (j) Dahl, O. Phosphorus and Sulfur 1983, 18, 201.
6. For examples of inversion of configuration at phosphine centers see: (a) Smith, D. J. H.; Trippett, S. J. Chem. Soc. Chem. Commun. 1969, 855. (b) Corfield, J. R.; Oram, R. K.; Smith D. J. H.; Trippett, S. J. Chem. Soc. Perkin Trans. 1, 1972, 713. (c) Kyba, E. P. J. Am. Chem. Soc. 1975, 97, 2554. (d) Kyba, E. P. J. Am. Chem. Soc. 1976, 98, 4805. (e) Omelanczuk, J.; Mikolajczyk, M. J. Chem. Soc. Chem. Commun. 1976, 1025. (f) Mikolajczyk, M.; Omelanczuk, J.; Perlikowska, W. Tetrahedron 1979, 35, 1531. (g) Mikolajczk, M. Pure Appl. Chem. 1980, 52, 959. (h) Nielsen, J.; Dahl, O. J. Chem. Soc. Perkin Trans. 2 1984, 553. (i) Dahl. O. Tetrahedron Lett. 1981, 22, 3281. (j) Dahl, O. Phosphorus and Sulfur 1983, 18, 201.
7. For examples of inversion of configuration at phosphine centers see: (a) Smith, D. J. H.; Trippett, S. J. Chem. Soc. Chem. Commun. 1969, 855. (b) Corfield, J. R.; Oram, R. K.; Smith D. J. H.; Trippett, S. J. Chem. Soc. Perkin Trans. 1, 1972, 713. (c) Kyba, E. P. J. Am. Chem. Soc. 1975, 97, 2554. (d) Kyba, E. P. J. Am. Chem. Soc. 1976, 98, 4805. (e) Omelanczuk, J.; Mikolajczyk, M. J. Chem. Soc. Chem. Commun. 1976, 1025. (f) Mikolajczyk, M.; Omelanczuk, J.; Perlikowska, W. Tetrahedron 1979, 35, 1531. (g) Mikolajczk, M. Pure Appl. Chem. 1980, 52, 959. (h) Nielsen, J.; Dahl, O. J. Chem. Soc. Perkin Trans. 2 1984, 553. (i) Dahl. O. Tetrahedron Lett. 1981, 22, 3281. (j) Dahl, O. Phosphorus and Sulfur 1983, 18, 201.
8. For examples of inversion of configuration at phosphine centers see: (a) Smith, D. J. H.; Trippett, S. J. Chem. Soc. Chem. Commun. 1969, 855. (b) Corfield, J. R.; Oram, R. K.; Smith D. J. H.; Trippett, S. J. Chem. Soc. Perkin Trans. 1, 1972, 713. (c) Kyba, E. P. J. Am. Chem. Soc. 1975, 97, 2554. (d) Kyba, E. P. J. Am. Chem. Soc. 1976, 98, 4805. (e) Omelanczuk, J.; Mikolajczyk, M. J. Chem. Soc. Chem. Commun. 1976, 1025. (f) Mikolajczyk, M.; Omelanczuk, J.; Perlikowska, W. Tetrahedron 1979, 35, 1531. (g) Mikolajczk, M. Pure Appl. Chem. 1980, 52, 959. (h) Nielsen, J.; Dahl, O. J. Chem. Soc. Perkin Trans. 2 1984, 553. (i) Dahl. O. Tetrahedron Lett. 1981, 22, 3281. (j) Dahl, O. Phosphorus and Sulfur 1983, 18, 201.
9. For examples of inversion of configuration at phosphine centers see: (a) Smith, D. J. H.; Trippett, S. J. Chem. Soc. Chem. Commun. 1969, 855. (b) Corfield, J. R.; Oram, R. K.; Smith D. J. H.; Trippett, S. J. Chem. Soc. Perkin Trans. 1, 1972, 713. (c) Kyba, E. P. J. Am. Chem. Soc. 1975, 97, 2554. (d) Kyba, E. P. J. Am. Chem. Soc. 1976, 98, 4805. (e) Omelanczuk, J.; Mikolajczyk, M. J. Chem. Soc. Chem. Commun. 1976, 1025. (f) Mikolajczyk, M.; Omelanczuk, J.; Perlikowska, W. Tetrahedron 1979, 35, 1531. (g) Mikolajczk, M. Pure Appl. Chem. 1980, 52, 959. (h) Nielsen, J.; Dahl, O. J. Chem. Soc. Perkin Trans. 2 1984, 553. (i) Dahl. O. Tetrahedron Lett. 1981, 22, 3281. (j) Dahl, O. Phosphorus and Sulfur 1983, 18, 201.
10. For examples of inversion of configuration at phosphine centers see: (a) Smith, D. J. H.; Trippett, S. J. Chem. Soc. Chem. Commun. 1969, 855. (b) Corfield, J. R.; Oram, R. K.; Smith D. J. H.; Trippett, S. J. Chem. Soc. Perkin Trans. 1, 1972, 713. (c) Kyba, E. P. J. Am. Chem. Soc. 1975, 97, 2554. (d) Kyba, E. P. J. Am. Chem. Soc. 1976, 98, 4805. (e) Omelanczuk, J.; Mikolajczyk, M. J. Chem. Soc. Chem. Commun. 1976, 1025. (f) Mikolajczyk, M.; Omelanczuk, J.; Perlikowska, W. Tetrahedron 1979, 35, 1531. (g) Mikolajczk, M. Pure Appl. Chem. 1980, 52, 959. (h) Nielsen, J.; Dahl, O. J. Chem. Soc. Perkin Trans. 2 1984, 553. (i) Dahl. O. Tetrahedron Lett. 1981, 22, 3281. (j) Dahl, O. Phosphorus and Sulfur 1983, 18, 201.
11. For examples of retention of configuration in nucleophilic attack in phosphines see: (a) Keglebich, G.; Quin, L. D. Phosphorus and Sulfur 1986, 26, 129. (b) Inch, T. D.; Hall, C. R. Tetrahedron Lett. 1976, 40, 3545.
12. For examples of retention of configuration in nucleophilic attack in phosphines see: (a) Keglebich, G.; Quin, L. D. Phosphorus and Sulfur 1986, 26, 129. (b) Inch, T. D.; Hall, C. R. Tetrahedron Lett. 1976, 40, 3545.
13. (a) Horner, J; Jordan, M. Phosphorus and Sulfur 1980, 8, 235.
14. (b) Mosho, J. A. Phosphorus and Sulfur 1978, 4, 273.
15. For examples of inversion in nucleophilic attack at phosphorus(V) see: (a) Korpiun, O.; Mislow, K. J. Am. Chem. Soc. 1967, 89, 4784. (b) Lewis, R. A.; Mislow, K. J. Am. Chem. Soc. 1969, 91, 7009. (c) Van der Berg, G. R.; Plantenburg, D. H. J. M.; Benschop, H. P. Recl. Trav. Chim. 1972, 91, 929. (d) Cullis, P. M.; Kaye, A. D. J. Chem. Soc. Chem. Commun. 1992, 346.
16. For examples of inversion in nucleophilic attack at phosphorus(V) see: (a) Korpiun, O.; Mislow, K. J. Am. Chem. Soc. 1967, 89, 4784. (b) Lewis, R. A.; Mislow, K. J. Am. Chem. Soc. 1969, 91, 7009. (c) Van der Berg, G. R.; Plantenburg, D. H. J. M.; Benschop, H. P. Recl. Trav. Chim. 1972, 91, 929. (d) Cullis, P. M.; Kaye, A. D. J. Chem. Soc. Chem. Commun. 1992, 346.
17. For examples of inversion in nucleophilic attack at phosphorus(V) see: (a) Korpiun, O.; Mislow, K. J. Am. Chem. Soc. 1967, 89, 4784. (b) Lewis, R. A.; Mislow, K. J. Am. Chem. Soc. 1969, 91, 7009. (c) Van der Berg, G. R.; Plantenburg, D. H. J. M.; Benschop, H. P. Recl. Trav. Chim. 1972, 91, 929. (d) Cullis, P. M.; Kaye, A. D. J. Chem. Soc. Chem. Commun. 1992, 346.
18. For examples of inversion in nucleophilic attack at phosphorus(V) see: (a) Korpiun, O.; Mislow, K. J. Am. Chem. Soc. 1967, 89, 4784. (b) Lewis, R. A.; Mislow, K. J. Am. Chem. Soc. 1969, 91, 7009. (c) Van der Berg, G. R.; Plantenburg, D. H. J. M.; Benschop, H. P. Recl. Trav. Chim. 1972, 91, 929. (d) Cullis, P. M.; Kaye, A. D. J. Chem. Soc. Chem. Commun. 1992, 346.
19. For examples of retention and inversion of configuration at phosphorus(V) see: (a) Harrison, J. M.; Inch, T. D. J. Chem. Soc. Perkin Trans. 1 1979, 2885. (b) Haarger, M. J. P. J. Chem. Soc. Perkin Trans. 1 1977, 2057.
20. For examples of retention and inversion of configuration at phosphorus(V) see: (a) Harrison, J. M.; Inch, T. D. J. Chem. Soc. Perkin Trans. 1 1979, 2885. (b) Haarger, M. J. P. J. Chem. Soc. Perkin Trans. 1 1977, 2057.
21. (a) Westheimer, F. H. Acc. Chem Res. 1968, 1, 70.
22. (b) Hengge, A. C.; Edens, W. A.; Elsing, H. J. Am. Chem. Soc. 1995, 116, 5045.
23. (c) Macomber, R. S. J. Am. Chem. Soc. 1983, 105, 4386.
24. (a) Rowell, R.; Gorenstein, D. G. J. Am. Chem. Soc. 1981, 103, 5894.
25. (b) DeBruin, K. E.; Zon, G.; Naumann, K.; Mislow, K. J. Am. Chem. Soc. 1969, 91, 7027.
26. Li, J; Beak, P. J. Am. Chem. Soc. 1992, 114, 9206.
27. For a detailed review of the endocyclic restriction test, see: Beak, P. Acc. Chem. Res. 1992, 25, 215.
28. Jugé, S.; Stephan, M. Laffitte, J. A.; Genet, J. P. Tetrahedron Lett. 1990, 31, 6357.
29. The configuration of (R)-19 has been established by X-ray crystallography: Jugé, S.; Stephans, M.; Genet, J. P.; Halut-Desportes, S.; Jeannin, S. Acta Crystallogr., Sect. C 1990, 46, 1869.
30. The stereochemical outcome of organolithium addition to (R)-19 has been established for the methyl and o-anisyl addition products by X-ray crystallography: Jugé, S.; Stephans, M.; Merdès, R.; Genet. J. P.; Halut-Desportes, S. J. Chem. Soc. Chem. Commun. 1993, 531.
31. 10
32. Imamoto, T.; Kusumoto, T.; Suzuki, N.; Sato, K. J. Am. Chem. Soc. 1985, 107, 5301.
33. Skowronska, A. Bull. De L'Academie Polanaise Des Sciences 1973, 21, 459.
34. Korpiun, O.: Lewis, R. A.; Chickos, J.; Mislow, K. J. Am. Chem. Soc. 1968, 90, 4842.
35. Dunach, E.; Kagen, H. B. Tetrahedron Lett. 1985, 26, 2649.
36. Horner, L. Pure Appl. Chem. 1964, 5, 225.
37. Other oxidants (m-CPBA and t-BuOOH) also provide retention of sterochemistry and gave similar results.
38. The endocyclic restriction test was attempted for a 15- and 18-membered endocyclic ring; however, only intermolecular t-butyl addition at phosphorus was observed.
39. Only one apical addition is shown, but an equivalent apical addition could occur to afford the naphthyl group and nucleophile in apical positions.
40. An intermediate similar to 41 has been observed by NMR: Ross. M. R.; Martin, J. C. J. Am. Chem. Soc. 1981, 103, 1234.
41. Berry, R. S. J. Chem. Phys. 1960, 32, 933.
42. (a) Corriu, R. J. P.; Guerin, C. In Advances in Organometallic Chemistry; Stone, F. G. A., West, R., Eds.; Academic Press: New York, 1982; p 265.
43. (b) Corriu, R. J. P.; Guerin, C. J. Organomet. Chem. 1980, 198, 231.
44. Mislow, K. Acc, Chem. Res. 1970, 3, 321.
45. (a) Sheldrick, W. S.; Schmidpeter, A.; Zwaschka, F.; Dillon, K. B.; Platt, A. W. G.; Waddington, T. C. J. Chem. Soc., Dalton Trans. 1981, 413.
46. (b) Lattman, M.; Olmstead, M. M.; Power, P. P.; Rankin, D. W. H.; Robertson, H. E. Inorg. Chem. 1988, 27, 3012.
47. Gillespie, R. J.; Hargittai, I. The VSEPR Model of Molecular Geometry: Allyn and Bacon: New York, 1991.
48. Bachrach, S. M.; Mulhearn, D. C. J. Chem. Phys. 1993, 97, 12229.
49. Bent, H. Chem. Rev. 1961. 61, 275.
50. Bondarenko, N. A.; Tsvetkov, E. N.; Matrozov, E. I.; Kabachnik, M. I. Izn. Akad. Nauk SSR, Ser. Khim. 1978, 2109.
51. Korpiun, O.; Lewis, R. A.; Chickos, J.; Mislow, K. J. Am. Chem. Soc. 1968, 90, 4842.