ORGANIC
LETTERS
2000
Vol. 2, No. 6
831-834
Hyperconjugative Control by Remote
Substituents of Diastereoselectivity in
the Oxygenation of Hydrocarbons
Mar´ıa E. Gonza´lez-Nun˜ez, Jorge Royo, Gloria Castellano, Cecilia Andreu,
Carmen Boix, Rossella Mello, and Gregorio Asensio*
Departamento de Qu´ımica Orga´nica, UniVersidad de Valencia,
AVda. V. Andre´s Estelle´s s/n, 46100-Burjassot (Valencia), Spain
gregorio.asensio@uV.es
Received January 24, 2000
ABSTRACT
The oxidation of 2-substituted adamantanes (2) with TFDO (1) is reported. The data show a stereodifferentiation of the chemical environments
induced by remote electron-withdrawing substituents which produces remarkable Z/E diastereoselectivity in the oxidation of the tertiary C −H
5
and C −H bonds. The results show a bell-shaped correlation between the Z/E stereoselectivity and the substituent constant σI, which is
7
interpreted in terms of hyperconjugative stabilization of the diastereomeric transition states.
Interpreting the effect of remote substituents on the diaste-
reoselectivity in chemical reactions by stereoelectronic factors
is an important subject in the field of organic chemistry.1
Many studies have been conducted on diastereoselectivity
in addition and elimination reactions as a consequence of
the different degrees of stabilization of transition states by
hyperconjugation.2 Examples include studies of the selectivity
of reactions3 such as ketone reduction and olefin epoxidation.
However, to the best of our knowledge, reports on the effects
of remote substituents on the reactivity of unactivated C-H
σ-bonds are scarce,3d most likely due to the lack of reactivity
of hydrocarbons which necessitates the use of drastic or
unusual reaction conditions.4 Recently, methyl(trifluoro-
methyl) dioxirane (TFDO) (1) has been revealed to be an
efficient reagent5 for electrophilic6 oxygen atom insertion
into unactivated C-H bonds of hydrocarbons under Very mild
Hanh, J. M.; le Noble, W. J. J. Am. Chem. Soc. 1992, 114, 1916. (f)
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Hayashi, O., Ed.; Academic Press: New York, 1974; p 405. (b) Guengerich,
F. P.; McDonald, T. L. Acc. Chem. Res. 1984, 17, 9. (c) Schneider, H.-J.;
Mu¨ller, W. J. Org. Chem. 1985, 50, 4609. (d) Hill, C. L. In AdVances in
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Science 1986, 231, 1108. (b) Eliel, E. L.; Wilen, S. H. Stereochemistry of
Organic Compounds; Wiley-Interscience: New York, 1994; pp 37-39. (c)
Adcock, W.; Cotton, J.; Trout, N. A. J. Org. Chem. 1994, 59, 1867. (d)
Coxon, J. M.; Houk, K. N.; Luibrand, R. T. J. Org. Chem. 1995, 60, 418.
(e) Vedejs, E.; Dent, W. H., III; Kendall, J. T.; Oliver, P. A. J. Am. Chem.
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(2) (a) Schleyer, P. v. R. J. Am. Chem. Soc. 1967, 89, 699, 701. (b)
Cherest, M.; Felkin, H.; Prudent, N. Tetrahedron Lett. 1968, 2199. (c) Anh,
N. T.; Eisenstein, O. NouV. J. Chem. 1977, 1, 61. (d) Cieplak, A. S. J. Am.
Chem. Soc. 1981, 103, 4540. (e) Cieplak, A. S.; Tait, B. D.; Johnson, C. R.
J. Am. Chem. Soc. 1989, 111, 8447.
(3) (a) Cheung, C. K.; Tseng, L. T.; Lin, M.-H.; Srivastava, S.; le Noble,
W. J. J. Am. Chem. Soc. 1986, 108, 1598. (b) Srivastava, S.; le Noble, W.
J. J. Am. Chem. Soc. 1987, 109, 5874. (c) Chung, W.-S.; Turro, N. J.;
Srivastava, S.; Li, H.; le Noble, W. J. J. Am. Chem. Soc. 1988, 110, 7882.
(d) Fukunishi, K.; Kohno, A.; Kojo, S. J. Org. Chem. 1988, 53, 4369. (e)
10.1021/ol000017m CCC: $19.00 © 2000 American Chemical Society
Published on Web 02/24/2000