Electrophilic aromatic chlorination and haloperoxidation of chloride catalyzed by polyfluorinated alcohols: A new manifestation of template catalysis

Journal of the American Chemical Society

Volumn 125, Issue 40, 2003, Pages 12116-12117

  Ben Daniel, Revital ^a   De Visser, Samuël P ^b   Shaik, Sason ^b   Neumann, Ronny ^a  

^a WEIZMANN INSTITUTE OF SCIENCE   (Israel)

^b HEBREW UNIVERSITY OF JERUSALEM   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL; ALCOHOL DERIVATIVE; ANISOLE; BENZENE; CHLORIDE; HALIDE; POLYCYCLIC AROMATIC HYDROCARBON; POLYFLUORINATED ALCOHOL; SOLVENT; TOLUENE; TRIFLUOROETHANOL; UNCLASSIFIED DRUG;

ARTICLE; CALCULATION; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHLORINATION; DIELECTRIC CONSTANT; EPOXIDATION; HALOGENATION; OXIDATION; PEROXIDATION;

EID: 0141957601     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0364524     Document Type: Article

References (22)

1. (a) Butler, A.: Walker, J. V. Chem. Rev. 1993, 93, 1937.
2. (b) Franssen, M. C. R.; van der Plas, H. C. Adv. Appl. Microbiol. 1992, 37, 41.
3. A few examples: (a) Sels, B.; de Vos, D.: Buntinx, M.; Pierard, F.; Krish-DeMesmaecker, A.; Jacobs, P. Nature 1999, 400, 855.
4. (b) Walker, J. V.; Morey, M.; Carlsson, H.; Davidson, A.; Stucky, G. D.; Butler, A. J. Am. Chem. 1997, 119, 6921.
5. (c) De la Rosa, R. I.; Clague, M. J.; Butler, A. J. Am. Chem. Soc. 1992, 114, 760.
6. (d) Colpas, G. J.: Hamstra, B. J.; Kampf, J. W.; Pecoraro, V. L. J. Am. Chem. Soc. 1996, 118, 3469.
7. (e) Clague, M. J.; Butler, A. J. Am. Chem. Soc. 1995, 117, 3475.
8. Barhate, N. B.; Gajare, A. S.; Wakharkar, R. D.; Bedekat, A. V. Tetrahedron Lett. 1998, 39, 6349.
9. +, may be considered, cf.: Swain, C. G.; Crist, D. R. J. Am. Chem. Soc. 1972, 94, 3195.
10. Held, A. M.; Halko, D. J.; Hurst, J. K. J. Am. Chem. Soc. 1978, 100, 5732.
11. (a) Neimann, K.; Neumann, R. Org. Lett. 2000, 2, 2861.
12. (b) van Vliet, M. C. A.; Arends, I. W. C. E.; Sheldon, R. A. Synlett 2001. 248.
13. (c) Legros, J.; Crousse. B.; Bonnet-Delpon, D.; Bégué, J.-P. Eur. J. Org. Chem. 2002. 3290.
14. A few examples: (a) Berkessel, A.; Andreae, M. R. M.; Schmickler, H.; Lex, J. Angew. Chem., Int. Ed. 2002, 41, 4481.
15. (b) van Vliet, M. C. A.; Arends, I. W. C. E.; Sheldon, R. A. Chem. Commun. 1999, 821.
16. (c) Iskra, J.; Bonnet-Delpon, D.; Bégué, J. P. Tetrahedron Lett. 2002, 43, 1001.
17. de Visser, S. P.; Kaneti, J.; Neumann, R.; Shaik, S. J. Org. Chem. 2003, 68, 2903.
18. Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry - Part A; Kluwer/Plenum: New York, 2000; p 575.
19. The reactivity trends as a function of the electronic properties of the substituents as well as the para directing effects of bulky substituents are clearly consistent with electrophilic substitution. The substrates,. for example, p-xylene or mesitylene, are not isomerized under the reaction conditions.
20. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin. K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.: Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; AI-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.7; Gaussian, Inc.: Pittsburgh, PA, 1998.
21. 8). Therefore, in all reactions, we focused on the bond activation step which is rate determining.
22. Similar effects on the TS and similar experimental rate constants were observed using hexafluoro-2-propanol instead of TFE as solvent.