978
LETTERS
SYNLETT
intermediate
compound.
b
undergoes decomposition to give the carbonyl
prakash, G. K.Synlett 1993, 427. (c) Bandgar, B. P.; Shaikh, S. I.;
Iyer, S.; Synth. Commun. 1996, 26, 1163 (c) Bose, D. S.; Srinivas,
P. Synth. Commun. 1997, 27, 3835.
10. (a) Curran, D. P.; Brill, J. F.; Rakiewicz, D. M. J. Org. Chem. 1984,
49, 1654. (b) Drabowicz, J. Synthesis, 1980, 125. (c) Corey, E. J.;
Hopkins, P. B.; Kim, S.; Yoo, S.; Nambiar, K. P.; Falck, J. R. J. Am.
Chem. Soc. 1979, 101, 7131.
11. Laszlo, P.; Polla, E. Synthesis 1985, 439.
12. Aizpurua, J. M.; Palomo, C. Tetrahedron Lett. 1983, 24, 4367.
13. Joseph, R.; Sudalai, A.; Ravindranathan, T. Tetrahedron Lett.,
1994, 35, 5493.
14. Curini, M.; Rosati, O.; Pisani, E. Synlett 1996, 333.
15. Bandgar, B. P.; Kunde, L. B.; Thote, J. L. Synth. Commun. 1997,
27, 1149.
Scheme 1
16. Ayhan, H. D.; Tanyeli, E. A. Tetrahedron Lett. 1997, 38, 7267.
17. Varma, R. S.; Meshram, H. M. Tetrahedron Lett. 1997, 38, 5427.
In conclusion, we have developed a facile method for the regeneration
of carbonyl compounds from both aldoximes, ketoximes and
tosylhydrazones which has wide scope, a simple procedure, high yields,
reduced reaction times and mild conditions. Further applications of this
reagent to many other types of organic functional group transformation
reactions are in progress.
18. Kumar, B.; Kumar, H.; Thakur, U, Kaur, B. Ind. J. Chem. 1991,
30B, 1069.
19. (a) Chidambaram, N.; Satyanarayana, K.; Chandrasekaran, S.
Synth. Commun. 1989, 19, 1727. (b) Olah, G. A.; Welch, J. J. Am.
Chem. Soc. 1978, 100, 5396.
20. Maloney, J. R.; Lyle, R. E.; Scavedra, J. E.; Lyle, G. G. Synthesis
1978, 212.
General procedure: To a stirred solution of oxime or tosylhydrazone
(3.0 mmol) in DMSO-THF (1:3, 3 mL) was added solid IBX (4.5 mmol)
in portions during 2-3 minutes. The suspension was vigorously stirred at
room temperature for specified time (Table 1). The reaction was
monitored by TLC. After completion, it was diluted with water (2x5
mL), the white precipitate was filtered off, and the reaction mixture was
extracted with ether (2x25 mL). The combined organic phase was
21. Drabowicz, J.; Synthesis 1980, 125.
22. Rao, C. G.; Radhakrishna, A. S.; Singh, B. B.; Bhatnagar, S. P.
Synthesis 1983, 808.
23. Aizpurua, J. M.; Juaristi, M.; Lecea, B.; Palomo, C. Tetrahedron
1985, 41, 2903.
washed with brine, dried (Na SO ) and the solvent was removed in
2
4
24. Dess, B. D.; Martin, J. C. J. Am. Chem. Soc. 1991, 113, 7277.
CAUTION: IBX was reported to be explosive under impact or
heating to >200°C by Plumb, J. B.; Harper, D. J. Chem. Eng. News
1990, July 16, 3.
vacuo to afford the crude product which was purified by column
chromatography on silica gel (E-Merck 60-120 mesh).
Authors wish to express sincere thanks to Dr. M.K. Gurjar for his keen
interest and encouragement in the work.
25. For
a most recent report using expensive 70% tert-butyl
hydroperoxide (TBHP), which required 8-18 hr for the completion
of the deoximation and constitutes a serious limitation to this
procedure, see Barhate, N. B.; Gajare, A. S.; Wakharkar, R. D.;
Sudalai, A. Tetrahedron Lett. 1997, 38, 653.
References and Notes:
† IICT Communication No. 3827
26. Garner, P.; Park, J. M.Org. Synth. 1992, 70, 18-24.
1.
Greene, T. G.; Wuts, P. G. M. Protective Groups in Organic
Synthesis 2nd Ed.; John Wiley & Sons, New York, 1991; pp. 175-
223.
27. All the products were characterized by IR, 1H NMR and mass
spectral data. The products 3b,4b,6b-10b melting points were
compared with authentic samples obtained from Aldrich and
Lancaster Chemical Co. L-oxazolidine Oxime 2a : [α]D-25.3° (c,
2.5, CHCl3) : 1H NMR (CDCl3) : δ 1.32 (s, 9 H), 1.38 (brs, 3 H),
1.55 (brs, 3 H), 3.72 (dd, 1 H, J = 8.7 and 8.3 Hz), 3.85 (dd, 1 H, J
= 8.7 and 2.9 Hz), 4.05-4.12 (m, 1 H), 6.71-6.83 (bs, 1 H), 7.29-
7.42 (m, 1 H). L-oxazolidine aldehyde 2b : [α]D -88.5° (c, 0.5,
2.
Whitesell, J. K.; Whitesell, M. A. Synthesis 1983, 517 and
references cited therein.
3.
4.
Donaruma, L. G.; Heldt, W. Z. Organic Reactions, 1960, 11, 1.
Cheronis, N. D.; Entrikin, J. B. Identification of organic
compounds, Interscience, New York, 1963.
1
CHCl3) : lit26 -91.7° (CHCl3, c 1.34), H NMR (CDCl3) : δ 1.35
5.
Lartey, P. A.; Faghih, R. Recent progress in the chemical
modification of erythromycin. In recent progress in the chemical
synthesis of antibiotics and related microbial products; Lukacs. G.
Ed.; Springer-Verlag: Berlin, 1993, vol. 2, pp.121-140.
(s, 9 H), 1.41 (bs, 3 H), 1.54 (bs, 3 H), 3.75 (dd, 1 H, J = 8.7 and
8.3 Hz), 3.92 (dd, 1 H, J = 8.7 and 2.9 Hz), 3.97-4.01 (m, 1 H),
9.54 (brs, 1 H). IR(neat) cm-1 : 1735, 1700. Oxime 5a : H NMR
1
(CDCl3) : δ 1.32 (s, 3 H), 1.50 (s, 3 H), 1.65 (s, 3 H), 1.72 (s, 3 H),
3.92-4.12 (m, 2 H), 4.23-4.25 (m, 1 H), 4.52-4.55 (m, 1 H), 5.18-
5.31 (m, 2 H), 5.95 (d, 1 H), 6.92 (d, 1 H), 8.45-8.61 (bs, 1 H). MS
(CI) m/z (relative intensity) : 271 (M+, 100%), 203 (42), 128 (21),
116 (55). [α]D -135° (c, 1.2, CHCl3). IR (neat) cm-1 : 3200, 1650.
Oxime 6a : 1H NMR (CDCl3) : δ 3.65 (s, 2 H), 3.78 (s, 2 H), 7.03-
7.35 (m, 3 H), 7.81 (m, 1 H). m.p. 132-135°C. lit. 134-135. Price,
C.C.; Hori, M.; Parasaran, T.; Polk, J. Am. Chem. Soc. 1963, 85,
2278.
6.
7.
8.
9.
(a) Barton, D. H. R.; Beaton, J. M.; Geller, L. E.; Pechet, M. M. J.
Am. Chem. Soc. 1961, 83, 4076, 4083.
Corey, E. J.; Niimura, K.; Konishi, Y.; Hashimoto, S.; Hamada, Y.
Tetrahedron Lett. 1986, 27, 2199.
Donaldson, R. E.; Saddler, J. C.; Byrn, S.; McKenzie, A. T.; Fuchs,
P.L. J. Org. Chem. 1983, 48, 2167.
(a) Barton, D. H. R.; Lester, D. J.; Ley, S. V. J. Chem. Soc. Chem.
Comm., 1977, 445. (b) Olah, G. A.; Liao, Q, Lee, C. S.;Surya