A novel type of nucleophilic substitution reactions on nonactivated aromatic compounds and benzene itself with trimethylsiliconide anions

Organic Letters

Volumn 3, Issue 8, 2001, Pages 1197-1200

  Postigo, Al ^a   Rossi, Roberta A ^a  

^a DEPARTAMENTO DE FISICOQUÍMICA   (Argentina)

Author keywords

[No Author keywords available]

Indexed keywords

ANION; BENZENE; FLUOROBENZENE; HEMPA; NITROBENZENE DERIVATIVE; SILICON;

ARTICLE; CHEMICAL MODEL; CHEMISTRY; TEMPERATURE; TIME;

ANIONS; BENZENE; FLUOROBENZENES; HEMPA; MODELS, CHEMICAL; NITROBENZENES; SILICON; TEMPERATURE; TIME FACTORS;

EID: 0035912324     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol015666s     Document Type: Article

References (39)

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20. The spectroscopic evidence agrees well with the published spectra, see: Freeburger, M. E.; Hughes, M.; Buell, G. R.; Tierman, T. O.; Splatter, L. J. Org. Chem. 1971, 36, 933. See also: Nishimura, J.; Fukurawa, J.; Kawabata, N. J. Organomet. Chem. 1971, 29, 237. Cartledge, F. K.; Riedel, K. H. J. Organomet. Chem. 1972, 34, 11. Moerlin, S. M. J. Organomet. Chem. 1987, 319, 29. Eaborn, C.; Jaura, K. L.; Walton, D. R. M. J. Chem. Soc. 1964, 1198.
21. The spectroscopic evidence agrees well with the published spectra, see: Freeburger, M. E.; Hughes, M.; Buell, G. R.; Tierman, T. O.; Splatter, L. J. Org. Chem. 1971, 36, 933. See also: Nishimura, J.; Fukurawa, J.; Kawabata, N. J. Organomet. Chem. 1971, 29, 237. Cartledge, F. K.; Riedel, K. H. J. Organomet. Chem. 1972, 34, 11. Moerlin, S. M. J. Organomet. Chem. 1987, 319, 29. Eaborn, C.; Jaura, K. L.; Walton, D. R. M. J. Chem. Soc. 1964, 1198.
22. The spectroscopic evidence agrees well with the published spectra, see: Freeburger, M. E.; Hughes, M.; Buell, G. R.; Tierman, T. O.; Splatter, L. J. Org. Chem. 1971, 36, 933. See also: Nishimura, J.; Fukurawa, J.; Kawabata, N. J. Organomet. Chem. 1971, 29, 237. Cartledge, F. K.; Riedel, K. H. J. Organomet. Chem. 1972, 34, 11. Moerlin, S. M. J. Organomet. Chem. 1987, 319, 29. Eaborn, C.; Jaura, K. L.; Walton, D. R. M. J. Chem. Soc. 1964, 1198.
23. The spectroscopic evidence agrees well with the published spectra, see: Freeburger, M. E.; Hughes, M.; Buell, G. R.; Tierman, T. O.; Splatter, L. J. Org. Chem. 1971, 36, 933. See also: Nishimura, J.; Fukurawa, J.; Kawabata, N. J. Organomet. Chem. 1971, 29, 237. Cartledge, F. K.; Riedel, K. H. J. Organomet. Chem. 1972, 34, 11. Moerlin, S. M. J. Organomet. Chem. 1987, 319, 29. Eaborn, C.; Jaura, K. L.; Walton, D. R. M. J. Chem. Soc. 1964, 1198.
24. The spectroscopic evidence agrees well with the published spectra, see: Freeburger, M. E.; Hughes, M.; Buell, G. R.; Tierman, T. O.; Splatter, L. J. Org. Chem. 1971, 36, 933. See also: Nishimura, J.; Fukurawa, J.; Kawabata, N. J. Organomet. Chem. 1971, 29, 237. Cartledge, F. K.; Riedel, K. H. J. Organomet. Chem. 1972, 34, 11. Moerlin, S. M. J. Organomet. Chem. 1987, 319, 29. Eaborn, C.; Jaura, K. L.; Walton, D. R. M. J. Chem. Soc. 1964, 1198.
25. Products 3a and 3b were quantified together. There is 3a:3b ratio of ca. 60:40.
26. Identified by GC-MS and compared with the authentic samples.
27. Determination of the relative concentrations of deuterated and nondeuterated products were carried out by GC/MS analysis (Shimadzu GC-17 A Series, DBS-MS 30 m x 0.2 mm x 0.18 mm film column, integrated to a Shimadzu GCMS-QP 5050A mass selective detector) by mass selective integration.
28. The spectroscopic evidence agrees well with the published spectra, see: Sulzbach, R. A. J. Organomet. Chem. 1970, 24, 307.
29. For the methyl chloroformate adduct, see: Fowler, F. J. Org. Chem. 1972, 37, 1321.
30. Taking only into account the ipso substitution product on substrate 2, i.e., 4, the relative reactivity is ca. 0.016.
31. 16d
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35. Pentacoordinated and other hypervalent states of silicon are well-known, see: Holmes, R. R. Chem. Rev. 1996, 96, 927. Chuit, C.; Corriu, J. P.; Reye, C.; Colin Young, J. Chem. Rev. 1993, 93, 1371. Anglada, J. M.; Bo, C.; Bofill, J. M.; Crehuet, R.; Poblet, J. M. Organometallics 1999, 18, 5584 and references therein.
36. Pentacoordinated and other hypervalent states of silicon are well-known, see: Holmes, R. R. Chem. Rev. 1996, 96, 927. Chuit, C.; Corriu, J. P.; Reye, C.; Colin Young, J. Chem. Rev. 1993, 93, 1371. Anglada, J. M.; Bo, C.; Bofill, J. M.; Crehuet, R.; Poblet, J. M. Organometallics 1999, 18, 5584 and references therein.
37. Pentacoordinated and other hypervalent states of silicon are well-known, see: Holmes, R. R. Chem. Rev. 1996, 96, 927. Chuit, C.; Corriu, J. P.; Reye, C.; Colin Young, J. Chem. Rev. 1993, 93, 1371. Anglada, J. M.; Bo, C.; Bofill, J. M.; Crehuet, R.; Poblet, J. M. Organometallics 1999, 18, 5584 and references therein.
38. Bunnett, J. F. Acc. Chem. Res. 1978, 11, 413.
39. By semiempirical methods (AM1) the energy of the pentacoordinate complex is much lower than that of the σ adduct (for PhF and PhI). The intermediate σ adduct does not exist (AM1) for PhCl and PhBr. Calculations at a higher level of theory are in progress for all the compounds in this system.