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combined organic layers were washed with brine, dried over
Na2SO4, filtered and evaporated under reduced pressure to give the
crude product. Purification by preparative thin-layer chromato-
7. Calvet, G.; Blanchard, N.; Kouklovsky, C. Synthesis 2005, 3346; Krchnak, V.;
Waring, K. R.; Noll, B. C.; Moellmann, U.; Dahse, H.-M.; Miller, M. J. J. Org. Chem.
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graphy (EtOAc/MeOH¼9:1) as eluent gave
(506 mg, 70%) as a blue-green oil that slowly crystallises to a green
solid. IR (neat),
(cmꢀ1): 2943, 2851, 2800, 1751, 1563, 1447, 1370,
1280, 1221, 1160, 1100, 1021. 1H NMR (300 MHz, CDCl3)
2.90–2.85
(m, 2H), 2.35 (s, 3H), 2.29–2.24 (m, 4H), 2.20 (s, 3H), 1.89–1.83 (m,
a-acetoxynitroso 42a
n
d
2H). 13C NMR (75 MHz, CDCl3)
d 168.7, 120.8, 50.9, 45.6, 29.3, 21.2.
Mp¼ 46–47 ꢂC. MS (CI, NH3) m/z 187 [(MþH)þ, 100]. HRMS (ESI):
calculated for C8H15N2O3 [MþH]þ: 187.1077, found: 187.1077.
4.1.12. 1-Methyl-4-nitroso-4-piperidinyl 4-chlorobenzoate (42b). [Bis-
(p-chlorobenzoyloxy)iodanyl]benzene 31e (2.00 g, 3.90 mmol) was
added in one portion to a stirred solution of 1-methyl-4-piperidinone
oxime58 (500 mg, 3.90 mmol) in CH2Cl2 (20 mL) at 0 ꢂC under argon.
After stirring at 0 ꢂC for 0.5 h, the resulting solution was allowed to
warmtortandstirredatrtforafurther6 h. Then, thereactionmixture
was poured into a saturated aqueous solution of NaHCO3 and the
layers were separated. The aqueous layer was extracted with CH2Cl2
and the combined organic layers were washed with brine, dried over
Na2SO4, filtered, and evaporated under reduced pressure to give the
crude product. Purification by flash chromatography on silica (EtOAc/
8. Calvet, G.; Blanchard, N.; Kouklovsky, C. Org. Lett. 2007, 9, 1485.
9. (a) Radical-mediated: Wu, M.; Begley, T. P. Org. Lett. 2000, 2, 1345; (b) Anionic-
mediated: Al-Harrasi, A.; Reissig, H.-U. Synlett 2005, 1152; (c) Lee, B. H.; Biswas,
A.; Miller, M. J. J. Org. Chem. 1986, 51, 106; (d) Labeeuw, O.; Phansavath, P.;
ˆ
Genet, J.-P. Tetrahedron Lett. 2004, 45, 7107; (e) Desai, M. C.; Doty, J. L.; Ste-
phens, L. M.; Brighty, K. E. Tetrahedron Lett. 1993, 34, 961; (f) Sodium or alu-
minum amalgam: Keck, G. E.; Fleming, S.; Nickell, D.; Weider, D. Synth.
Commun. 1979, 281; (g) Zinc in acetic acid: Baggiolini, E. G.; Lee, H. L.; Pizzolato,
G.; Uskokovic, M. R. J. Am. Chem. Soc. 1982, 104, 6460; (h) LiAlH4: Oppolzer, W.;
Petrzilka, M. J. Am. Chem. Soc. 1976, 98, 6722; (i) NiCl2/LiAlH4: Tuffariello, J. J.;
Meckler, H.; Pushpananda, K.; Seranatne, A. Tetrahedron 1985, 41, 3447; (j)
Molybdenum complex: Cicchi, S.; Goti, A.; Brandi, A.; Guarna, A.; De Sarlo, F.
Tetrahedron Lett. 1990, 31, 3351; (k) For the NaBH4 modification of Mo(CO)6, see:
Zhang, D.; Su¨ lling, D.; Miller, M. J. J. Org. Chem. 1998, 63, 885; (l) For the catalytic
Mo(CO)6 procedure, see: Li, F.; Brogan, J. B.; Gage, J. L.; Zhang, D.; Miller, M. J. J.
Org. Chem. 2004, 69, 8854538; (m) Samarium complex: Keck, E.; McHardy, S. F.;
Wager, T. T. Tetrahedron Lett. 1995, 36, 7419; (n) Indium: Cicchi, S.; Bonani, M.;
Cardona, F.; Revuelta, J.; Goti, A. Org. Lett. 2003, 5, 1773 Catalytic hydrogenation
over Pd/C, Pd(OH)2, PtO2 or Raney Ni: (o) Wovkulich, P. M.; Uskokovic, M. R. J.
Am. Chem. Soc. 1981, 103, 3956; (p) DeShong, P.; Leginus, J. M. J. Am. Chem. Soc.
1983, 105, 1686; (q) Lebel, N. A.; Ojha, N. D.; Menke, J. R.; Newland, R. J. J. Org.
Chem. 1972, 37, 2896; (r) Koizumi, T.; Hirai, H.; Yoshii, E. J. Org. Chem. 1982, 47,
MeOH¼9:1) as eluent gave
a
n
-acyloxynitroso 42b (535 mg, 48%) as
(cmꢀ1): 3429, 2942, 1723, 1594, 1564,
8.03 (d,
a bright blue solid. IR (neat),
1457,1443,1401,1284,1162,1090.1H NMR (360 MHz, CDCl3)
d
J¼8.8 Hz, 2H), 7.48 (d, J¼8.8 Hz, 2H), 3.05–2.95 (2H), 2.49–2.35 (7H
including 2.41 (s 3H)), 2.10–2.02 (2H). 13C NMR (90 MHz, CDCl3)
d
163.2, 140.1, 131.3, 128.9, 127.9, 121.1, 51.1, 45.6, 29.3. Mp¼ 90–92 ꢂC.
MS (CI, NH3) m/z 285 [(M (37Cl)þH)þ, 33], 283 [(M (35Cl)þH)þ, 100].
HRMS (ESI): calculated for C13H16ClN2O3 [MþH]þ: 283.0844, found:
283.0849.
4004; (s) For the first purely organic
s(N–O) bond scission, see: Galvani, G.;
Calvet, G.; Blanchard, N.; Kouklovsky, C. Org. Biomol. Chem. 2008, 6, 1063.
10. Braun, H.; Felber, H.; Kresze, G.; Schmidtchen, F. P.; Prewo, R.; Vasella, A. Liebigs
Ann. Chem. 1993, 261; Defoin, A.; Sifferlen, T.; Streith, J. Synlett 1997, 1294;
Defoin, A.; Sifferlen, T.; Streith, J. Tetrahedron 1997, 53, 13769; Defoin, A.;
Sarazin, H.; Streith, J. Tetrahedron 1997, 53, 13783; Bach, P.; Bols, M. Tetrahedron
Lett. 1999, 40, 3461.
Acknowledgements
11. Morley, A. D.; Hollinshead, D. M.; Procter, G. Tetrahedron Lett. 1990, 31, 1047.
12. Aoyagi, S.; Tanaka, R.; Naruse, M.; Kibayashi, C. Tetrahedron Lett. 1998, 39, 4513.
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14. Nitsch, H.; Kresze, G. Angew. Chem., Int. Ed. Engl. 1976, 15, 760.
We thank the MRES for a grant (GC), the University Paris-Sud
´
and the CNRS for financial support, Dr. Regis Guillot for the X-ray
structure of azodioxy 36 and A. Benelhadj for the IR/NMR studies of
dienophiles 22a and 37 with Zn(OTf)2. The authors warmly thank
Dr. R. Lett and Prof. Y. Langlois for their continuous support, stim-
ulating insights and careful proofreading of this manuscript.
15. (a) Felber, H.; Kresze, G.; Braun, H.; Vasella, A. Tetrahedron Lett. 1984, 25, 5381;
(b) Felber, H.; Kresze, G.; Prewo, R.; Vasella, A. Helv. Chim. Acta 1986, 69, 1137;
(c) Gouverneur, V.; McCarthy, S. J.; Mineur, C.; Belotti, D.; Dive, G.; Ghosez, L.
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Supplementary data
Supplementary data associated with this article can be found, in
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