PAPER
A Mild, Chemoselective, Oxidative Method For Deoximation Using Dess–Martin Periodinane
763
Table 2 Chemoselectivity – Oximes Verses Alcohols using DMPa
Substrates
DMP
equiv)
Products
Yield
(%)
b,c
(
(
(
i) 4-Chlorobenzaldoxime
ii) Octanol
1
(i) 4-chlorobenzaldehyde
(ii) unaffected
93
–
2
1
.2
.2
(i) 4-chlorobenzaldehyde
92
91
(ii) Octanal
(
(
i) Cyclohexanone oxime
ii) Benzyl alcohol
(i) Cyclohexanone
(ii) unaffected
92
–
2
1
(i) Cyclohexanone
92
90
(ii) Benzaldehyde
(i) Benzaldoxime
(i) Benzaldehyde
(ii) unaffected
92
–
(ii)1-Phenylethanol
2
.2
.2
(i) Benzaldehyde
92
90
(ii) Acetophenone
Benzoin oxime
1
2
Benzoin
Benzil
94
92
a
All reactions were carried out as in general procedure, by adding the specified quantities of DMP to a solution of oxime and alcohol (1:1) in
wet CH Cl (CH Cl saturated with water) at 5ºC→r.t. and stirred for 20 min.
2
2
2
2
b
c
Yields refer to pure isolated products by column chromatography.
Products were characterised by IR, H NMR.
1
1
H NMR (60 MHz, CDCl ): δ = 7.2–8.3 (m, 5H, ArH), 9.9 (s, 1H,
3
Acknowledgement
CHO).
We gratefully acknowledge the UGC of India for financial support
under COSIST program and fellowship to SSC.
Deoximation of Methyl 2-Oximino-1-phenylacetate
Gave methyl 2-oxo-1-phenylacetate; yield: 295 mg (90%) on col-
umn chromatography (silica gel; 30% EtOAc/hexane); colourless
oily liquid; (Lit.8 oily liquid).
a
References
–
1
IR (CHCl ): ν = 3035, 2930, 1732, 1691, 1590, 816, 740 cm .
(1) Green, T. W.; Wuts, P. G. M. Protective Groups in Organic
Synthesis, Wiley: New York, 1991, p 214.
3
1
H NMR (60 MHz, CDCl ): δ = 3.8 (s, 3H, OCH ), 7.2 (m, 3H,
3
3
(
2) (a) Morimoto, S.; Adachi, T.; Matsunaga, T.; Kashimura, M.;
Watanabe, Y.; Sota, K. Jpn Kokai Tokkyo Koho JP63-183597
ArH), 7.8 (m, 2H, ArH).
(
(
1
1998), (Chem Abstr. 1986, 109, 6898q).
b) Corey, E. J.; Petrzilka, M.; Ueda, Y. Helv. Chim. Acta.
977, 60, 2994.
Deoximation of 2-oximino-1-phenylpropan-1-one
Gave 1-phenylpropane-1,2-dione; yield: 278 mg (94%) on column
chromatography (Silica gel; 40% EtOAc/hexane); yellow oil; (Lit.
yellow oil).
8
a
(
3) Kabalka, G. W.; Pace, R. D.; Wadgaonkar, P. P. Synth.
Commun. 1990, 20, 2453.
IR (CHCl ): ν = 3027, 2942, 1702, 1673, 1598, 1320, 1043, 730,
6
(4) (a) Donaldson, R.; Sadler, J. C.; Boyrn, S.; Mckenzie,
A.T.; Fuchs, P. L. J. Org. Chem. 1983, 48, 2167.
(b) Drabowicz, J. Synthesis 1980, 125.
3
67cm–
1.
1
H NMR (60 MHz, CDCl ): δ = 2.5 (s, 3H, CH ), 7.5 (m, 3H, ArH),
3
3
(
c) Coery, E. J.; Hopkins, P. B.; Kim, S.; Kou, S.; Nambiar, K.
P.; Flack, J. R. J. Am. Chem. Soc. 1979, 101, 7131.
d) Curran, D. P.; Brill, J. F.; and Rakiewicz, D. M. J. Org.
Chem. 1984, 49, 1654.
e) Araujo, H. C.; Ferriera, G. A.; Mahajan, J. R. J. Chem. Soc.
Perkin Trans. I 1974, 2257.
f) Maloney, J. R.; Lyle, R. E.; Scavendra, J. E.; and Lyle, G.
7
.9 (m, 2H, ArH).
(
Deamidoximation of 3,3-Diphenylpropionamidoxime
Reaction was carried out at 0–5 °C; gave 3,3-diphenylpropion-
amide; yield: 405 mg (90%) on column chromatography (silica gel
(
3
(
0% EtOAc/haxane); white crystalline solid from EtOH; mp 124°C
(
Lit.8b mp 125 °C).
G. Synthesis 1978, 212.
IR(KBr): ν = 3401, 3360, 3000, 2902, 1672, 1593, 1447, 1213,
(g) Rao, C. G.; Rdhakrishan, A. H.; Singh, B. B.; Bhatnagar,
S. P. Synthesis 1983, 808.
–1
1
029,762, 699 cm .
1
(h) Aizpurua, J. M.; Juaristi, M.; Lecea, B.; and Palomo, C.
Tetrahedron Lett. 1985, 41, 2903. i) Lazlo, P.; Polla, E. Syn-
thesis 1985, 439.
H NMR (60 MHz, CDCl ): δ = 2.9 (t, J = 7 Hz, 1H, CH), 4.5 (d, J
3
=
7Hz, 2H, CH ), 7.2–7.9 (m, 10H, ArH).
2
(
2
j) Shim, S. B.; Kim, K.; Kim, Y. H. Tetrahedron Lett. 1987,
8, 645.
Synthesis 1999, No. 5, 760–764 ISSN 0039-7881 © Thieme Stuttgart · New York