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T. Caruso et al. / Tetrahedron 62 (2006) 2350–2356
H-18); 13C NMR (100 MHz, CDCl3): d 160.3 (HCO), 72.8
(C-2), 68.8 (C-3), 56.5, 56.4, 55.1, 42.7, 40.7, 40.1, 39.9,
39.6, 36.2, 35.8, 35.4, 34.9, 31.9, 29.7, 28.7, 28.2, 28.0,
24.2, 23.9, 22.8, 22.6, 20.9, 18.7, 14.4, 12.1; IR (CHCl3):
1720 cmK1 (formate ester signal). ESI-MS for C28H48O3
(m/z): Mr (calcd) 432.36, Mr (found) 455.19 (MCNa)C.
Anal. Calcd: C 77.72, H 11.18. Found: C 77.40, H 11.09.
13. Manzo, E.; Molinaro, A.; Bedini, E.; De Castro, C.; Parrilli, M.
Carbohydr. Res. 2001, 333, 339–342.
14. Kajimura, A.; Sumaoka, J.; Komiyama, M. Carbohydr. Res.
1998, 309, 345–351.
15. The excess of acid scavenger was evaluated respect to the total
concentration of HC of the solution, measured by titrimetry.
16. Krishnamurthy, S. S.; Soundararajan, S. 1st Proc. Chem. Symp.,
Chemistry and Metallurgy Comm. of the Dep. of Atomic
Energy, Bombay, 1970; Book of Abstracts, pp 261–264.
17. Sondu, S.; Sethuram, B.; Rao, N. T. Oxid. Commun. 1984, 7,
223–233.
Compound 6. [a]D C16 (c 0.7, CH2Cl2). MpZ90–91 8C. 1H
NMR (400 MHz, CDCl3): d 5.08 (br s, 1H, H-2), 4.02 (br s,
1H, H-3), 1.92 (m, 1H, H-1), 1.73 (m, 1H, H-4), 1.70–1.47
(m, 8H), 1.45–1.19 (m, 8H), 1.15–0.95 (m, 12H), 0.90 (m,
6H, H-19, H-21), 0.87 (2d, 6H, JZ6.0 Hz, H-26, H-27),
0.65 (s, 3H, H-18); 13C NMR (100 MHz, CDCl3): d 82.0
(C-2), 66.1 (C-3), 56.4, 56.2, 54.8, 42.6, 39.9, 39.5, 38.4,
36.4, 36.2, 35.8, 35.4, 35.0, 32.2, 31.8, 29.7, 28.2, 28.0,
24.1, 23.8, 22.8, 22.5, 20.8, 18.7, 13.4, 12.1; IR (CHCl3):
1629 and 1263 cmK1 (nitrate ester signals). ESI-MS for
C27H47NO4 (m/z): Mr (calcd) 449.35, Mr (found) 472.27
(MCNa)C. Anal. Calcd: C 72.12, H 10.54, N 3.11. Found:
C 72.17, H 10.51, N 3.08.
18. As suggested by a referee, the inclusion of an acid scavenger
(potassium carbonate or pyridine) might be expected to
attenuate also the Lewis acidity of the Ce(IV), and suppress
an eventual Lewis-acid mediated glycolysis pathway; never-
theless the hard character of this Lewis acid means that any
reduction in Lewis acidity would be minimal with these
additives used.
19. The attempt to see an acidic proton signal in the CAN(III)
DMF-d7 solution was initially unsuccessful, probably due to
the presence of water of crystallization, which was then
removed by oven drying the salt sample and adding powdered
˚
4 A molecular sieves to the NMR tube.
20. Zhang, Y.; Flowers, R. A., II J. Org. Chem. 2003, 68,
4560–4562.
References and notes
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two signals, as could be expected taking into account the
possibility of a slow interconversion of the two rotamers,
typical for tertiary amides, might be explained suggesting the
presence of a very predominant rotamer. Actually molecular
models obtained by MM2 force field calculations suggested
the presence of an electrostatic attraction between the
carboxylic oxygen and the positive-charged nitrogen of nitrate,
for only one rotamer, which should be the predominant one.
22. Rudd, E. J.; Finkelstein, M.; Ross, S. D. J. Org. Chem. 1972,
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