Towards a general scale of nucleophilicity?

Angewandte Chemie - International Edition

Volumn 45, Issue 23, 2006, Pages 3869-3874

  Phan, Thanh Binh ^a   Breugst, Martin ^a   Mayr, Herbert ^a  

^a UNIVERSITY OF MUNICH   (Germany)

Author keywords

Kinetics; Linear free energy relationships; Nucleophiles; Reaction mechanisms; Reactivity scales

Indexed keywords

CORRELATION METHODS; POSITIVE IONS; RATE CONSTANTS;

LINEAR FREE ENERGY RELATIONSHIPS; NUCLEOPHILES; REACTIVITY SCALES;

REACTION KINETICS;

EID: 33746238128     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200600542     Document Type: Article

References (75)

1. Nucleophilicity (Eds.: M. Harris, S. P. McManus), American Chemical Society, Washington, DC, 1987, (Adv. Chem. Ser. 215).
2. C. G. Swain, C. B. Scott, J. Am. Chem. Soc. 1953, 75, 141-147.
3. a) J. O. Edwards, J. Am. Chem. Soc. 1954, 76, 1540-1547;
4. b) J. O. Edwards, J. Am. Chem. Soc. 1956, 78, 1819-1820.
5. J. F. Bunnett, Annu. Rev. Phys. Chem. 1963, 14, 271-290; see also reference [1].
6. N in Equation (3) are both termed s. Because use of the same symbol for different properties would lead to confusion herein, we have modified the symbols used in the literature.
7. R. G. Pearson, H. Sobel, J. Songstad, J. Am. Chem. Soc. 1968, 90, 319-326.
8. a) C. D. Ritchie, Acc. Chem. Res. 1972, 5, 348-354;
9. b) C. D. Ritchie, P. O. I. Virtanen, J. Am. Chem. Soc. 1972, 94, 4966-4971.
10. L. A. P. Kane-Maguire, E. D. Honig, D. A. Sweigart, Chem. Rev. 1984, 84, 525-543.
11. R. D. Pike, D. A. Sweigart, Coord. Chem. Rev. 1999, 187, 183-222.
12. a) H. Mayr, T. Bug, M. F. Gotta, N. Hering, B. Irrgang, B. Janker, B. Kempf, R. Loos, A. R. Ofial, G. Remennikov, H. Schimmel, J. Am. Chem. Soc. 2001, 123, 9500-9512;
13. b) For a comprehensive listing of nucleophilicity parameters N and electrophilicity parameters E, see http://www.cup.uni-muenchen.de/oc/mayr/ DBintro.html.
14. a) H. Mayr, M. Patz, Angew. Chem. 1994, 106, 990-1010;
15. Angew. Chem. Int. Ed. Engl. 1994, 33, 938-957;
16. b) H. Mayr, B. Kempf, A. R. Ofial, Acc. Chem. Res. 2003, 36, 66-77;
17. c) H. Mayr, A. R. Ofial in Carbocation Chemistry (Eds.: G. A. Olah, G. K. S. Prakash), Wiley, Hoboken, NJ, 2004, chap. 13, pp. 331-358;
18. d) H. Mayr, A. R. Ofial, Pure Appl. Chem. 2005, 77, 1807-1821.
19. a) T. Tokuyasu, H. Mayr, Eur. J. Org. Chem. 2004, 2791-2796;
20. b) A. D. Dilman, H. Mayr, Eur. J. Org. Chem. 2005, 1760-1764.
21. a) A. D. Dilman, S. L. Ioffe, H. Mayr, J. Org. Chem. 2001, 66, 3196-3200;
22. b) B. Kempf, N. Hampel, A. R. Ofial, H. Mayr, Chem. Eur. J. 2003, 9, 2209-2218.
23. F. Dulich, K.-H. Müller, A. R. Ofial, H. Mayr, Helv. Chim. Acta 2005, 88, 1754-1768.
24. a) H. Mayr, K.-H. Müller, Collect. Czech. Chem. Commun. 1999, 64, 1770-1779;
25. b) H. Mayr, O. Kuhn, C. Schlierf, A. R. Ofial, Tetrahedron 2000, 56, 4219-4229.
26. T. Bug, M. Hartnagel, C. Schlierf, H. Mayr, Chem. Eur. J. 2003, 9, 4068-4076.
27. a) R. Lucius, H. Mayr, Angew. Chem. 2000, 112, 2086-2089;
28. Angew. Chem. Int. Ed. 2000, 39, 1995-1997;
29. b) R. Lucius, R. Loos, H. Mayr, Angew. Chem. 2002, 114, 97-102;
30. Angew. Chem. Int. Ed. 2002, 41, 91-95.
31. T. Bug, T. Lemek, H. Mayr, J. Org. Chem. 2004, 69, 7565-7576.
32. T. Bug, H. Mayr, J. Am. Chem. Soc. 2003, 125, 12 980-12 986.
33. S. Minegishi, H. Mayr, J. Am. Chem. Soc. 2003, 125, 286-295.
34. S. Minegishi, S. Kobayashi, H. Mayr, J. Am. Chem. Soc. 2004, 126, 5174-5181.
35. T. B. Phan, H. Mayr, Can. J. Chem. 2005, 83, 1554-1560.
36. B. Kempf, H. Mayr, Chem. Eur. J. 2005, 11, 917-927.
37. R. Loos, S. Kobayashi, H. Mayr, J. Am. Chem. Soc. 2003, 125, 14 126-14 132.
38. A. A. Tishkov, H. Mayr, Angew. Chem. 2005, 117, 145-148;
39. Angew. Chem. Int. Ed. 2005, 44, 142-145.
40. S. Minegishi, R. Loos, S. Kobayashi, H. Mayr, J. Am. Chem. Soc. 2005, 127, 2641-2649.
41. A. A. Tishkov, U. Schmidhammer, S. Roth, E. Riedle, H. Mayr, Angew. Chem. 2005, 117, 4699-4703;
42. Angew. Chem. Int. Ed. 2005, 44, 4623-4626.
43. H. Mayr, G. Lang, A. R. Ofial, J. Am. Chem. Soc. 2002, 124, 4076-4083.
44. H. Mayr, N. Basso, G. Hagen, J. Am. Chem. Soc. 1992, 114, 3060-3066.
45. H. Mayr, N. Basso, Angew. Chem. 1992, 104, 1103-1105;
46. Angew. Chem. Int. Ed. Engl. 1992, 31, 1046-1048.
47. M. A. Funke, H. Mayr, Chem. Eur. J. 1997, 3, 1214-1222.
48. T. Lemek, H. Mayr, J. Org. Chem. 2003, 68, 6880-6886.
49. a) F. Terrier, S. Lakhdar, R. Goumont, T. Boubaker, E. Buncel, Chem. Commun. 2004, 2586-2587;
50. b) F. Terrier, S. Lakhdar, T. Boubaker, R. Goumont, J. Org. Chem. 2005, 70, 6242-6253.
51. G. Ya. Remennikov, B. Kempf, A. R. Ofial, K. Polborn, H. Mayr, J. Phys. Org. Chem. 2003, 16, 431-437.
52. D. N. Kevill in Advances in Quantitative Structure-Property Relationship, Vol. 1 (Ed.: M. Charton), JAI, Greenwich, 1996, pp. 81-115.
53. D. N. Kevill, S. W. Anderson, J. Org. Chem. 1991, 56, 1845-1850.
54. T. B. Phan, H. Mayr, Eur. J. Org. Chem. 2006, in press.
55. T. B. Phan, H. Mayr, J. Phys. Org. Chem. 2006, in press.
56. B. Denegri, S. Minegishi, O. Kronja, H. Mayr, Angew. Chem. 2004, 116, 2353-2356;
57. Angew. Chem. Int. Ed. 2004, 43, 2302-2305.
58. N = 0.92 from ref. [21] were used.
59. a) A. Pross in Theoretical and Physical Principles in Organic Reactivity, Wiley, New York, 1995, p. 232;
60. b) S. Hoz in Nucleophilicity (Eds.: M. Harris, S. P. McManus), American Chemical Society, Washington, DC, 1987, pp. 181-194.
61. J. Koskikallio, Acta Chem. Scand. 1969, 23, 1477-1489.
62. C. D. Ritchie, Can. J. Chem. 1986, 64, 2239-2250.
63. J. W. Bunting, J. M. Mason, C. K. M. Heo, J. Chem. Soc. Perkin Trans. 2 1994, 2291-2300.
64. J. P. Richard, M. M. Toteva, J. Crugeiras, J. Am. Chem. Soc. 2000, 122, 1664-1674.
65. T. B. Phan, H. Mayr, unpublished results.
66. N N. For the same reasons discussed for Equation (3) (see ref. [11]), the parameters E′ and N′ are less convenient in practical use. Hence, we prefer to use the version of Equation (6) shown in Scheme 1.
67. a) C. D. Ritchie, J. Am. Chem. Soc. 1975, 97, 1170-1179;
68. b) C. D. Ritchie, M. Sawada, J. Am. Chem. Soc. 1977, 99, 3754-3761;
69. c) C. D. Ritchie, J. E. Van Verth, P. O. I. Virtanen, J. Am. Chem. Soc. 1982, 104, 3491-3497;
70. d) C. D. Ritchie, J. Am. Chem. Soc. 1984, 106, 7187-7194.
71. H. Mayr, Angew. Chem. 1990, 102, 1415-1428;
72. Angew. Chem. Int. Ed. Engl. 1990, 29, 1371-1384.
73. a) The Anomeric Effect and Associated Stereoelectronic Effects (Ed.: G. R. J. Thatcher), ACS Symp. Ser. 1993, 539;
74. b) E. Juaristi, G. Cuevas, Tetrahedron 1992, 48, 5019-5087.
75. C. D. Ritchie, P. O. I. Virtanen, J. Am. Chem. Soc. 1972, 94, 1589-1594.