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N.; Hu, B.; Hu, X. J. Org. Chem. 2007, 72, 4288–4291. (d) Wang, N.;
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(31) The use of AcOH as a solvent did not promote racemization
either. MeCN gave the corresponding aldehyde in higher yield.
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(33) 11 was not obtained after the reaction under 9/NaNO2
conditions. Metal-salt-free conditions promoted the production of 11.
(34) The details are provided in the Supporting Information.
(35) (a) Rychnovsky, S. D.; Vaidyanathan, R.; Beauchamp, T.; Lin,
R.; Farmer, P. J. J. Org. Chem. 1999, 64, 6745–6749. (b) Bobbitt, J. M.;
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(15) 1-Me-AZADO (4) also catalyzed the oxidation of menthol with
moderate efficiency under Liu and Liang’s conditions (FeCl3/NaNO2/O2/
CH2Cl2).9d It was found that AcOH realizes nonmetal aerobic oxidation,
while FeCl3 is necessary to have the reaction proceed in CH2Cl2.
(16) It is presumed that the oxidation rate of 5,7-diF-AZADOH by
NO2 decreases because of the increasing oxidation potential.
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(36) The reference electrode was Ag/AgCl.
(18) 5-F-AZADOþNO3 (11): IR (neat) νmax: 1628, 1372,
ꢀ
1333 cmꢀ1. ESI-MS(þ): m/z 170 [5-F-AZADO]þ. ESI-MS(ꢀ): m/z
62 [NO3]ꢀ. Anal. Calcd for C9H13FN2O4: C, 46.55; H, 5.64; N, 12.06.
Found: C, 46.26; H, 5.73; O, 11.86. The counteranion of 5-F-AZADOþ
was also identified as NO3ꢀ by ion chromatography.
(19) In DSC analysis, the starting point of exothermic decomposi-
tion was 116 °C, and the amount of heat released was 1815 J/g. These
data do not suggest the necessity of careful operation involving 11 to
prevent explosion in laboratory-scale operation.34
(20) 9 was easily prepared from 2-azaadamantane by a five-step
method that we have established as a kilogram-scale preparation
procedure (WO 2009/066735).34
(21) Tables showing the effect of AcOH are provided in the
Supporting Information. They indicate that the use of AcOH as a
solvent is not essential for these aerobic oxidation systems: addition of
2ꢀ5 equiv of AcOH in MeCN completed the aerobic oxidation using 1
mol % 9 and 10 mol% NaNO2, and 5 mol % 11 realized the aerobic
oxidation under AcOH-free conditions.34
(22) 11 was easily prepared either by mixing 9 and HNO3 in Et2O or
by treatment with NO2 gas.34
(23) 11 was stable enough to handle in air.
(24) Yamakoshi, H.; Shibuya, M.; Tomizawa, M.; Osada, Y.; Kanoh,
N.; Iwabuchi, Y. Org. Lett. 2010, 12, 980–983.
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(27) In accordance with the comment of one of the reviewers, we
attempted the 0.1 mol scale oxidation of 1,2:4,5-di-O-isopropylidene-β-
D-fructopyranose (22a). Because of an efficient electron transfer system,
the reaction proceeded smoothly to give the product in high yield
without pressurized oxygen.34
(28) (a) Hattori, H.; Nozawa, E.; Iino, T.; Yoshimura, Y.; Shuto, S.;
Shimamoto, Y; Nomura, M.; Fukushima, M.; Tanaka, M.; Sasaki, T.;
Matsuda, A. J. Med. Chem. 1998, 41, 2892–2902. (b) Yoshimura, Y.;
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dx.doi.org/10.1021/ja110940c |J. Am. Chem. Soc. 2011, 133, 6497–6500