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Consistent with the proposed mechanism is the observed
increase in the proportion of the Z-isomer in the course
of formation of 2-methyl-3-phenyloxaziridine (vide
supra).
Interestingly, H-bonding solvents and Lewis agents
increase the rate of formation of oxaziridine (Tables
2 and 3). EtOH with highest ability for H-bonding
among the solvents used in this study and BF3ÆEt2O as
the strongest Lewis acid are the most effective ones in
this regard. These results may reflect the extent of their
specific interactions with the coordinated HSOꢂ5 , which
may contribute to both O–O bond cleavage and sta-
bilization of the leaving anionic group (HSOꢂ4 ).
14. Boyd, D. R.; Jennings, W. B.; McGuckin, R. M.;
Rutherford, M.; Saket, B. M. J. Chem. Soc., Chem.
Commun. 1985, 582–583.
15. Kloc, K.; Kubicz, E.; Mlochowski, J.; Syper, L. Synthesis
1987, 1084–1087.
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Andre, C. Chem. Eur. J. 1997, 3, 1691–1709.
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18. Schirmann, J.-P.; Weiss, F. Tetrahedron Lett. 1972, 633–
634.
19. Kraiem, J.; Kacem, Y.; Khiari, J.; Hassine, B. B. Synth.
Commun. 2001, 31, 263–271.
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Synlett 2002, 933–934.
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F. B.; Rafikov, S. R. Tetrahedron Lett. 1971, 2807–2808.
22. Auret, B. J.; Boyd, D. R.; Coulter, P. B. J. Chem. Soc.,
Chem. Commun. 1984, 463–464.
23. Martiny, L.; Jørgensen, K. A. J. Chem. Soc., Perkin Trans.
1 1995, 699–704.
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Reddy, T. J. Org. Chem. 1988, 53, 2087–2089.
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26. Campestrini, S.; Meunier, B. Inorg. Chem. 1992, 31, 1999–
2006. It is notable that freshly prepared TBAO displayed
much stronger oxidizing ability than commercially avail-
able samples. Caution: this peroxide should be considered
as a potential explosive.
It is noteworthy that, while TBAO in combination with
manganese meso-tetraphenylporphyrin acts as an effec-
tive and selective catalytic system for epoxidation of
alkenes,35 the same system yielded oxaziridines with low
selectivity. For instance, complete oxidation of entry 1
resulted in only 46% oxaziridine and 54% of the corre-
sponding aldehyde within 10 min.
In conclusion, this report presents a single phase, inex-
pensive, and very simple method for the synthesis of
oxaziridines with excellent yields and selectivity under
mild reaction conditions.
Acknowledgements
27. (a) The aldimines were prepared according to the litera-
ture: Ref. 17 herein; (b) Campbell, K. N.; Sommers, A. H.;
Campbell, B. K. J. Am. Chem. Soc. 1944, 66, 82–84; (c)
Tiollais, M. R. Bull. Soc. Chim. Fr. 1947, 708, 959–968; (d)
Layer, R. W. Chem. Rev. 1962, 62, 489–510.
28. In a general procedure, TBAO (1 mmol) was added to a
solution of aldimines (1 mmol) in CH3CN (5 mL) and
stirred under air, at room temperature. The formation of
oxaziridine and the consumption of the starting aldimine
were monitored by TLC and 1H NMR. After vacuum
evaporation of the solvent at room temperature, the
product was extracted with CCl4.
29. Jennings, W. B.; Boyd, D. R.; Watson, C. G.; Becker, E.
D.; Bradley, R. B.; Jerina, D. M. J. Am. Chem. Soc. 1972,
94, 8501–8504.
30. Boyd, D. R.; Neil, D. C.; Watson, C. G. J. Chem. Soc.,
Perkin Trans. 2 1975, 1813–1818.
31. Madam, V.; Clapp, L. B. J. Am. Chem. Soc. 1969, 91,
6078–6083.
32. (a) Ogata, Y.; Sawaki, Y. J. Am. Chem. Soc. 1973, 95,
4687–4692; (b) J. Am. Chem. Soc. 1973, 95, 4692–4698.
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1979, 101, 1107–1109.
34. Bjørgo, J.; Boyd, D. R.; Watson, C. G.; Jennings, W. B.;
Jerina, D. M. J. Chem. Soc., Perkin Trans. 2 1974, 1081–
1084.
This work was supported by Shiraz University Research
Council.
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