1962
B. R. Buckley et al. / Tetrahedron: Asymmetry 21 (2010) 1959–1962
O
O
i) Me-NH2, EtOH
AcCl, MeOH,
Ph
OMe
.HCl
Ph
O
OH
ii) NaHCO3 (sat. aq.)
Δ, 2 h
NH2
99%
NH2
17
O
O
i) 4-MeOC6H4CHO
MeOH
Me
SOCl2, CH2Cl2
Ph
Me
Me
N
O
Ph
N
H
Ph
PMB
N
H
0ºC - r.t.
N
S
ii) NaBH4
NH2
NH
19 54%
PMB
18 h
18 62%
20 48%
Scheme 7. Synthesis of the thiadiazol-3-one 1-oxide 20.11
Löwgren, S.; Österlund, K.; Atepo, J.; Unge, T.; Hultén, J.; Bonham, N. M.; Schaal,
W.; Karlén, A.; Hallberg, A. J. Med. Chem. 1997, 40, 898.
compound 20 was an oil and we have as yet been unsuccessful in
determining the absolute stereochemistry at the sulfur. By 1H and
13C NMR spectroscopy, compound 20 appears to be a single
diastereoisomer.
5. Castro, J. L.; Matassa, V. G.; Ball, R. G. J. Org. Chem. 1994, 59, 2289.
6. (a) Ahn, K.-H.; Yoo, D.-J.; Kim, J.-S. Tetrahedron Lett. 1992, 33, 6661; (b) Pansare,
S. V.; Rai, A. N.; Kate, S. N. Synlett 1998, 623; (c) Sartor, D.; Saffrich, J.;
Helmchen, G.; Richards, C. J.; Lambert, H. Tetrahedron: Asymmetry 1991, 2, 639;
(d) Oppolzer, W.; Starkemann, C.; Rodriguez, I.; Bernadinelli, G. Tetrahedron
Lett. 1991, 32, 61; (e) Oppolzer, W.; Kingma, A. J.; Pillai, S. K. Tetrahedron Lett.
1991, 32, 4893.
3. Conclusion
7. Richey, H. G., Jr.; Farkas, J., Jr. J. Org. Chem. 1987, 52, 479.
We have successfully synthesized the first example of an
enantiomerically pure C2 symmetric benzothiadiazole 2-oxide.
We have also prepared the first thiatriaza-indene 3-oxide and
thiadiazol-3-one 1-oxide systems chiral at the sulfur atom in high
diastereoselectivity. We shall now endeavor to apply these and the
related systems in asymmetric catalysis.
8. (a) Dewynter, G.; Ubaldi, S.; Voyer, N.; Toupet, L. Tetrahedron Lett. 1998, 39,
7434; (b) Boudjabi, S.; Dewynter, G.; Voyer, N.; Toupet, L. Eur. J. Org. Chem.
1999, 9, 2275; (c) Regainia, Z.; Abdaoui, M.; Aouf, N. E.; Dewynter, G.; Montero,
J. L. Tetrahedron 2000, 56, 381.
9. Buckley, B. R.; Neary, S. P. Adv. Synth. Catal. 2009, 351, 71.
10. Rivas, F. M.; Riaz, U.; Giessert, A.; Smulik, J. A.; Diver, S. T. Org. Lett. 2001, 3,
2673.
11. All novel compounds were characterized by melting point, specific rotation,
infra red, combustion analysis, 1H and 13C NMR spectroscopy, mass
spectrometry, and accurate mass analysis.
Acknowledgments
12. For the synthesis and use of related C2 symmetric carbene ligands/catalysts see
for example: (a) Duguet, N.; Campbell, C. D.; Slawin, A. M. Z.; Smith, A. D. Org.
Biomol. Chem. 2008, 6, 1108; (b) Seiders, T. J.; Ward, D. W.; Grubbs, R. H. Org.
Lett. 2001, 3, 3225; (c) Chaulagain, M. R.; Sormunen, G. J.; Montgomery, J. J. Am.
Chem. Soc. 2007, 129, 9568.
The authors would like to thank Loughborough University for
funding a Ph.D. studentship (SPN) and Research Councils UK for a
RCUK fellowship (BRB).
13. Struble, J. R.; Kaeobamrung, J.; Bode, J. W. Org. Lett. 2008, 10, 957.
14. Knight, R. L.; Leeper, F. J. J. Chem. Soc., Perkin 1 1998, 1891.
15. (a) Enders, D.; Breuer, K.; Runsink, J.; Teles, J. H. Helv. Chim. Acta 1996, 79, 1899;
(b) Enders, D.; Kallfass, U. Angew. Chem., Int. Ed. 2002, 41, 1743.
16. (a) Kerr, M. S.; Read de Alaniz, J.; Rovis, T. J. Am. Chem. Soc. 2002, 124, 10298; (b)
Kerr, M. S.; Read de Alaniz, J.; Rovis, T. J. Org. Chem. 2005, 70, 5725.
17. For related C2 symmetric N-heterocyclic carbene examples see: (a) Cardinal-
David, B.; Raup, D. E. A.; Scheidt, K. A. J. Am. Chem. Soc. 2010, 132, 5345. and
references cited therein; (b) Li, G.-Q.; Dai, L.-X.; You, S.-L. Org. Lett. 2009, 11,
1623; (c) Zhang, Y.-R.; He, L.; Wu, X.; Shao, P. L.; Ye, S. Org. Lett. 2008, 10, 277;
(d) Concellón, C.; Duguet, N.; Smith, A. D. Adv. Synth. Catal. 2009, 351, 3001. and
references cited therein.
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18. Crystal data for enantiopure 13: C16H15N3O2S, M = 313.37, monoclinic, P21,
a = 7.3744(4), b = 8.8835(5), c = 12.0593(7) Å, b = 105.7428(8)°, V = 760.38(7) Å3,
Z = 2, Dc = 1.369 g cmÀ3 ) = 0.223 mmÀ1, T = 150(2) K, colorless plate,
, l(Mo Ka
1.05 Â 0.61 Â 0.06 mm3; 8881 reflections measured as above; 4509 inde-
pendent, data corrected as above (min. and max. transmission factors: 0.800,
0.987), Rint = 0.0168, structure solved by direct methods, F2 refinement,
R1 = 0.0323 for 4266 data with F2 > 2 (F2), wR2 = 0.0826 for all data; 199
r
parameters; absolute structure parameter x = À0.01(5). CCDC 783758 contain
the supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data Centre via