A. Sudo et al. / Tetrahedron Letters 44 (2003) 7889–7891
7891
lyzed the reaction at room temperature to give the
corresponding 5-membered cyclic dithiourethane, 4-
methyl-1,3-thiazolidine-2-thione (2). No regioisomer
4. Saito, S.; Nakagawa, S.; Koizumi, T.; Hirayama, K.;
Yamamoto, Y. J. Org. Chem. 1999, 64, 3975–3978.
5. Shen, Y. M.; Duan, W. L.; Shi, M. J. Org. Chem. 2003,
68, 1559–1562.
1
was detected by GC or by 300 MHz H NMR analysis
of the crude mixture. Similarly to the CO -fixation,
bromide was found to be a suitable anionic component
of catalysts for the present reaction. The reaction was
6. Darensbourg, D. J.; Lewis, S. J.; Rodgers, J. L.;
Yarbrough, J. C. Inorg. Chem. 2003, 42, 581–589.
2
7
8
9
. Calo, V.; Nacci, A.; Monopoli, A.; Fanizzi, A. Org. Lett.
2002, 4, 2561–2563.
. Paddock, R. M.; Nguyen, S. B. T. J. Am. Chem. Soc.
found to be much faster than the CO -fixation. Actu-
2
ally, it does not take 24 h for complete conversion of
MeAz at room temperature when lithium bromide was
used as a catalyst: We found that it was completely
converted to 2 by GC analysis of the reaction mixture
at 30 min. Furthermore, the reaction proceeded
smoothly even at −40°C to give 2 quantitatively within
2
001, 123, 11498–11499.
. Nozaki, K.; Nakano, K.; Hiyama, T. J. Am. Chem. Soc.
999, 121, 11008–11009.
0. Kihara, N.; Hara, N.; Endo, T. J. Org. Chem. 1993, 58,
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1. Kawanami, H.; Ikushima, Y.; Torii, K. Tetrahedron Lett.
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2. Tascedda, P.; Dunach, E. Chem. Commun. 2000, 11,
49–450.
1
1
1
1
1
6
30 min. Further study on kinetics of the reaction is
needed.
2
In summary, cycloadditions of CO and its sulfur ana-
2
4
logue, CS2, with aziridine were found to be hopeful
candidates as methods for their chemical fixation. The
fixations can be operated under atmospheric pressure at
room temperature by employing alkali metal halide or
quaternary ammonium salt as a catalyst, which are
stable and easily handled. The present systems will be
further improved to be ideally environmentally friendly
ones by more detailed studies on reaction mechanism
and further optimization of the conditions. Similar
reactions of aziridines having various substituents are
under investigation to clarify the scope and limitation
of the present system.
3. Banks, M. R.; Cadogan, J. I. G.; Gosney, I.; Hodgson, P.
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9
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