Angewandte
Chemie
[
5] In the original literature, s’E in Equation (1) and sN in Equa-
tion (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.
[
6] R. G. Pearson, H. Sobel, J. Songstad, J. Am. Chem. Soc. 1968, 90,
319 –326.
[
7] a) C. D. Ritchie, Acc. Chem. Res. 1972, 5, 348 –354; b) C. D.
Ritchie, P. O. I. Virtanen, J. Am. Chem. Soc. 1972, 94, 4966 –
4
971.
8] L. A. P. Kane-Maguire, E. D. Honig, D. A. Sweigart, Chem. Rev.
984, 84, 525 –543.
9] R. D. Pike, D. A. Sweigart, Coord. Chem. Rev. 1999, 187, 183 –
22.
[
[
1
2
[
10] 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; b) For a comprehensive
listing of nucleophilicity parameters N and electrophilicity
parameters E, see http://www.cup.uni-muenchen.de/oc/mayr/
DBintro.html.
[
11] a) H. Mayr, M. Patz, Angew. Chem. 1994, 106, 990 –1010;
Angew. Chem. Int. Ed. Engl. 1994, 33, 938 –957; b) H. Mayr, B.
Kempf, A. R. Ofial, Acc. Chem. Res. 2003, 36, 66 – 77; 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 –
Scheme 1. General equation [Eq. (6)] for electrophile–nucleophile com-
binations and its relation to other more specialized correlation
equations.
3
1
58; d) H. Mayr, A. R. Ofial, Pure Appl. Chem. 2005, 77, 1807 –
821.
have not yet been explored. As the nucleophilicity parameters
N and sN have been derived from reactions with carbon
electrophiles whereas the electrophilicity parameters E and sE
have been derived from reactions with carbon nucleophiles,
Equation (6) should only be applied to reactions where at
least one of the reaction centers in either electrophile or
nucleophile is carbon. Even then, deviations are to be
expected, if stabilizing or destabilizing geminal substituent
interactions are created or destroyed in the transition state.
Thus, carboxonium ions react faster with alcohols than
predicted by Equations (3) or (6) (anomeric product stabili-
[
12] a) T. Tokuyasu, H. Mayr, Eur. J. Org. Chem. 2004, 2791 –2796;
b) A. D. Dilman, H. Mayr, Eur. J. Org. Chem. 2005, 1760 –1764.
[13] a) A. D. Dilman, S. L. Ioffe, H. Mayr, J. Org. Chem. 2001, 66,
196 –3200; b) B. Kempf, N. Hampel, A. R. Ofial, H. Mayr,
3
Chem. Eur. J. 2003, 9, 2209 –2218.
[
[
14] F. Dulich, K.-H. Müller, A. R. Ofial, H. Mayr, Helv. Chim. Acta
2
005, 88, 1754 –1768.
15] a) H. Mayr, K.-H. Müller, Collect. Czech. Chem. Commun. 1999,
4, 1770 –1779; b) H. Mayr, O. Kuhn, C. Schlierf, A. R. Ofial,
Tetrahedron 2000, 56, 4219 –4229.
6
[16] T. Bug, M. Hartnagel, C. Schlierf, H. Mayr, Chem. Eur. J. 2003, 9,
4068 –4076.
[17] a) R. Lucius, H. Mayr, Angew. Chem. 2000, 112, 2086 –2089;
Angew. Chem. Int. Ed. 2000, 39, 1995 –1997; b) R. Lucius, R.
Loos, H. Mayr, Angew. Chem. 2002, 114, 97 –102; Angew. Chem.
Int. Ed. 2002, 41, 91 –95.
18] T. Bug, T. Lemek, H. Mayr, J. Org. Chem. 2004, 69, 7565 –7576.
19] T. Bug, H. Mayr, J. Am. Chem. Soc. 2003, 125, 12980 –12986.
20] S. Minegishi, H. Mayr, J. Am. Chem. Soc. 2003, 125, 286 –295.
21] S. Minegishi, S. Kobayashi, H. Mayr, J. Am. Chem. Soc. 2004,
126, 5174 –5181.
[
50]
zation). On the other hand, Ritchieꢀs observation that the
N+ parameters for heteronucleophiles defined by Equa-
tion (2) are also applicable to reactions with diazonium
[
7,43,51]
ions
indicates that in certain cases Equation (6) may
[
[
[
[
also hold for combinations of heteroelectrophiles with
heteronucleophiles.
We hope that the possibility to describe a large variety of
organic reactions by a single empirical correlation [Eq. (6)]
will stimulate further activities to unveil the physical basis of
electrophilicity and nucleophilicity.
[22] T. B. Phan, H. Mayr, Can. J. Chem. 2005, 83, 1554 –1560.
23] B. Kempf, H. Mayr, Chem. Eur. J. 2005, 11, 917 –927.
24] R. Loos, S. Kobayashi, H. Mayr, J. Am. Chem. Soc. 2003, 125,
[
[
1
4126 –14132.
Received: February 9, 2006
Published online: April 28, 2006
[
[
[
25] A. A. Tishkov, H. Mayr, Angew. Chem. 2005, 117, 145 –148;
Angew. Chem. Int. Ed. 2005, 44, 142 –145.
26] S. Minegishi, R. Loos, S. Kobayashi, H. Mayr, J. Am. Chem. Soc.
2005, 127, 2641 –2649.
27] A. A. Tishkov, U. Schmidhammer, S. Roth, E. Riedle, H. Mayr,
Angew. Chem. 2005, 117, 4699 –4703; Angew. Chem. Int. Ed.
Keywords: kinetics · linear free energy relationships ·
.
nucleophiles · reaction mechanisms · reactivity scales
2
005, 44, 4623 –4626.
28] H. Mayr, G. Lang, A. R. Ofial, J. Am. Chem. Soc. 2002, 124,
076 –4083.
[
4
[
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; b) J. O.
Edwards, J. Am. Chem. Soc. 1956, 78, 1819 –1820.
[29] H. Mayr, N. Basso, G. Hagen, J. Am. Chem. Soc. 1992, 114,
3060 –3066.
[30] H. Mayr, N. Basso, Angew. Chem. 1992, 104, 1103 –1105; Angew.
Chem. Int. Ed. Engl. 1992, 31, 1046 –1048.
[
[
[
4] J. F. Bunnett, Annu. Rev. Phys. Chem. 1963, 14, 271 –290; see
also reference [1].
[31] M. A. Funke, H. Mayr, Chem. Eur. J. 1997, 3, 1214 –1222.
[32] T. Lemek, H. Mayr, J. Org. Chem. 2003, 68, 6880 –6886.
Angew. Chem. Int. Ed. 2006, 45, 3869 –3874
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3873