A pragmatic procedure for predicting regioselectivity in nucleophilic substitution of aromatic fluorides

Tetrahedron Letters

Volumn 52, Issue 24, 2011, Pages 3150-3153

  Liljenberg, Magnus ^a   Brinck, Tore ^b   Herschend, Björn ^c   Rein, Tobias ^c   Rockwell, Glen ^c   Svensson, Mats ^c  

^a ASTRAZENECA R AND D   (Sweden)

^b ROYAL INSTITUTE OF TECHNOLOGY   (Sweden)

^c ASTRAZENECA R AND D   (Sweden)

Author keywords

Complex; Computational; DFT; Nucleophilic substitution; Regioselectivity

Indexed keywords

ANION; AROMATIC COMPOUND; FLUORIDE; NUCLEOPHILE;

ACCURACY; ARTICLE; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; DENSITY FUNCTIONAL THEORY; ISOMER; MOLECULAR STABILITY; NUCLEOPHILICITY; QUANTITATIVE ANALYSIS; REGIOSELECTIVITY; SUBSTITUTION REACTION;

EID: 79956042668     PISSN: 00404039     EISSN: 18733581     Source Type: Journal    
DOI: 10.1016/j.tetlet.2011.04.032     Document Type: Article

References (33)

1. M. Liljenberg, T. Brinck, B. Herschend, T. Rein, G. Rockwell, and M. Svensson J. Org. Chem. 14 2010 4696 4705
2. J. March Advanced Organic Chemistry second ed. 1984 McGraw-Hill International Book Company
3. R.W. Hoffman Dehydrobenzene and Cycloalkynes 1967 Academic Press New York
4. R. Frlan, and D. Kikelj Synthesis 2006 2271 2285
5. B.H. Yang, and S.L. Buchwald J. Organomet. Chem. 576 1999 125 146
6. L. Jiang, and S.L. Buchwald A. de Meijere, F. Diederich, Metal-Catalysed Cross-Coupling Reactions 2nd ed. 2004 Wiley-VCH Verlag GmbH Weinheim, Germany 699 760
7. J.A. Zoltewicz Top. Curr. Chem. 59 1975 33 64
8. J. Miller Aromatic Nucleophilic Substitution 1968 Elsevier Amsterdam
9. J. Burdon Tetrahedron 21 1965 3373 3380
10. J. Burdon, and I.W. Parsons J. Am. Chem. Soc. 99 1977 7445 7447
11. N.J. Epiotis, and W. Cherry J. Am. Chem. Soc. 98 1976 5432 5435
12. F.A. Bulat, E. Chamorro, P. Fuentealba, and A. Toro-Labbe J. Phys. Chem. A 108 2004 342 349
13. R.K. Roy, S. Krishnamurti, P. Geerlings, and S. Pal J. Phys. Chem. A 102 1998 3746 3755
14. C. Morell, A. Grand, and A. Toro-Labbe J. Phys. Chem. A 109 2005 205 212
15. T. Giroldo, L.A. Xavier, and J.M. Riveros Angew. Chem., Int. Ed. 43 2004 3588 3590
16. M.N. Glukhovtsev, R.D. Bach, and S. Laiter J. Org. Chem. 62 1997 4036 4046
17. M. Muir, and J. Baker J. Fluorine Chem. 126 2005 727 738
18. J. Baker, and M. Muir Can. J. Chem. 88 2010 588 597
19. L.V. Politanskaya, L.A. Malysheva, I.V. Beregovaya, I.Y. Bagryanskaya, Y.V. Gatilov, E.V. Malykhin, and V.D. Shteingarts J. Fluorine Chem. 126 2005 1502 1509
20. Jaguar, version 7.0; Schrödinger, LLC: New York, 2007.
21. 1.
22. Sodium methoxide in methanol at rt. R.D. Chambers, W.K.R. Musgrave, and P.G. Urben J. Chem. Soc., Perkin Trans. 1 1974 2580 2584
23. 3 in acetonitrile at 0 °C. R.E. Banks, A. Prakash, and N.D. Venayak J. Fluorine Chem. 16 1980 325 338
24. Sodium methoxide in methanol at rt. D.R. Chambers, M.J. Seabury, D.L.H. Williams, and N. Hughes J. Chem. Soc., Perkin Trans. 1 1988 255 257
25. 3 in acetone/water at reflux J.F.W. Keana J. Org. Chem. 55 1990 3640 3647
26. In order to measure the accuracy, we calculated the energy differences between the two experimentally determined major isomers and the corresponding differences for the proposed method. For each reaction, we then calculated the deviation between the experimental energy difference and the calculated energy difference, and so obtained the average absolute deviation.
27. Provided that these reactions will proceed at all - this model has nothing to say about absolute reaction rates.
28. This could be an indication that for some reactions involving sulfur nucleophiles, TS modeling is required to achieve high accuracy. We will return to this question in forthcoming work.
29. O. Acevedo, and W.L. Jorgensen Org. Lett. 6 2004 2881 2884
30. Benzyl alcohol with excess NaH in THF at rt overnight. R. Dirr, C. Anthaume, and L. Desaubry Tetrahedron Lett. 49 2008 4588 4590
31. Sodium methoxide in methanol at rt. D.R. Chambers, M.J. Seabury, and D.L.H.J. Williams Chem. Soc., Perkin Trans. 1 1988 251 254
32. Sodium methoxide in methanol at -82 to -84 °C (entry 6). Sodium hydrosulfide (NaHS) in DMF and ethylene glycol at -5 to 2 °C (entry 7). Sodium methanethiolate in ethanol at -85 to -90 °C (entry 8). Brooke, G. M.; Chambers, R. D.; Drury, C. J.; Bower, M. J. J. Chem. Soc., Perkin Trans. 1, 1993, 2201-2209.
33. R.D. Chambers, P.A. Martin, G. Sandford, and D.L.H. Williams J. Fluorine Chem. 129 2008 998 1002