8750
R. S. Ribeiro et al. / Tetrahedron Letters 48 (2007) 8747–8751
12. Barluenga, J.; Marco-Arias, M.; Gonzales-Bobes, F.;
´
on the crude reaction products by the analytical proce-
dures employed (HRGC–MS, 1H NMR and 13C
NMR spectroscopy). As previously observed,23 excep-
tions were observed in the reactions with 1-octene that
produced a mixture of regioisomers in which the pri-
mary iodide predominated (Table 1, entries 13 and
14). High trans-stereoselectivity was also observed for
additions to cyclohexene and 1-methycyclohexene
(Table 1, entries 7–12).
´
Ballesteros, A.; Gonzales, J. M. Chem. Eur. J. 2004, 10,
1677.
13. Kolvani, E.; Ghorbani-Choghamarani, A.; Salehi, P.;
Shirini, F.; Zolfigol, M. A. J. Iran. Chem. Soc. 2007, 4,
126.
14. de Souza, S. P. L.; da Silva, J. F. M.; de Mattos, M. C. S.
Quim. Nova 2006, 29, 1061.
15. (a) Vankar, Y. D.; Kumaravel, G. Tetrahedron Lett. 1984,
25, 233; (b) Sniady, A. Synlett 2006, 960; (c) de Mattos, M.
C. S.; Bernini, R. B. Heterocycl. Commun. 2006, 12,
411.
16. Dolenc, D. Synlett 2000, 544; Urankar, D.; Rutar, I.;
Modec, B.; Dolenc, D. Eur. J. Org. Chem. 2005, 2349.
Enolethers (2 mmol) reacted quickly and smoothly with
TICA (0.67 mmol) at room temperature in MeOH to
produce the corresponding iodo-dialkylacetals (Table
2, entries 1–3).30 However, if the reaction was performed
with 1-methoxycyclohexene in water, the hemiacetal was
very unstable and 2-iodocyclohexanone was obtained in
69% yield (entry 4).
17. Mendonc¸a, G. F.; Magalhaes, R. M.; de Mattos, M. C. S.;
˜
Esteves, P. M. J. Braz. Chem. Soc. 2005, 16, 695;
Mendonc¸a, G. F.; Sanseverino, A. M.; de Mattos, M. C.
S. Synthesis 2003, 45; Wengert, M.; Sanseverino, A. M.; de
Mattos, M. C. S. J. Braz. Chem. Soc. 2002, 13, 700.
18. De Almeida, L. S.; Esteves, P. M.; de Mattos, M. C. S.
Synlett 2006, 1515; de Almeida, L. S.; Esteves, P. M.; de
Mattos, M. C. S. Synthesis 2006, 221; Tozetti, S. D. F.; de
Almeida, L. S.; Esteves, P. M.; de Mattos, M. C. S. J.
Braz. Chem. Soc. 2007, 18, 675; de Almeida, L. S.; Esteves,
P. M.; de Mattos, M. C. S. Synlett 2007, 1687.
In conclusion, we have presented an efficient and eco-
friendly alternative reagent for the regioselective coio-
dination of alkenes, affording good to excellent yields
of iodohydrins, b-iodoethers and b-iodoacetates under
mild conditions.
19. Sanseverino, A. M. Quim. Nova 2000, 23, 102.
20. Gottardi, W. Monatsh. Chem. 1970, 101, 655.
21. Procedure for the preparation of TICA. Iodine
(184.6 mmol, 46.85 g) and trichloroisocyanuric acid
(55.93 mmol, 13.00 g) were added to a 100 mL sealed tube
and heated in a sand bath at 180 ꢁC. After 24 h, the ICl
produced was distilled off under reduced pressure and the
sealed tube was heated again at 230 ꢁC during 48 h.
Evaporation of ICl under reduced pressure and heating
gave triiodoisocyanuric acid as a brown solid in 90% yield.
At room temperature TICA decomposes slowly with the
formation of I2. On the other hand, in the presence of light
the decomposition is very fast. However, if stored in dark
in a freezer, TICA proved to be stable for at least one year.
IR (cmÀ1): m 3211, 3053, 2884, 2830, 2780, 1700, 1665,
1459, 1372, 1145, 1061, 1051, 732, 663, 533.20
Acknowledgements
The authors thank CNPq, CAPES and FAPERJ for the
financial support. We also thank Professor Vitor Fran-
cisco Ferreira and Mrs. Sabrina Baptista Ferreira (Insti-
tuto de Quımica/UFF) for the kind donation of butyl
vinyl ether. One of the referees is also acknowledged
for useful suggestions.
´
References and notes
22. General procedure for coiodination of alkenes. To a stirred
solution of the alkene (2 mmol) in an appropriated solvent
(8 mL of acetone and 4 mL of H2O for iodohydrins, or
10 mL of alcohols or acetic acid for b-iodoethers and b-
iodoacetates), TICA (0.67 mmol) was added at room
temperature. The reaction was monitored by HRGC–MS.
After the specified time shown in Table 1 (for alkenes),
CH2Cl2 (10 mL) was added, cyanuric acid was filtered off
and the resulting solution was treated with 10% aq
NaHSO3 (50 mL). The aqueous phase was washed with
CH2Cl2 (2 · 10 mL), the organic extract was dried (anhy-
drous Na2SO4) and filtered. The solvent was evaporated
on a rotatory evaporator to give the pure product.
23. Sanseverino, A. M.; de Mattos, M. C. S. Synth. Commun.
1998, 28, 559.
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