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and a catalytic amount of pyridinium p-toluenesulfonate (PPTS,
0.20 g) was stirred at room temperature for 2 h. The produced
MeOH was removed subsequently in vacuo. The resulting slurry
of the crude orthoesters (36.5 g) could be used without any
purication in the next step.
For analytical purposes, K2CO3 (0.30 g) was added to the
mixture before distilling it through a Vigreux-column (15 cm) in
vacuo. Aer removal of MeOH (40 ꢀC, 250 mbar), 28.2 g (78%) of
a mixture of the two orthoesters 9a (trans) and 9b (cis) (74 ꢀC, 1
ꢁ 10ꢂ3 mbar) was obtained as a colorless liquid. Distillation at
temperatures higher than 150 ꢀC should be avoided as this can
cause polymerization of the mixture. The two orthoesters 9a,b
are mixtures of trans/cis diastereomers.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
¨
Financial support by the State of Baden-Wurttembert, Germany
and the DAAD (PPP Brasilien 2018, project-ID: 57391106) is
gratefully acknowledged. We also thank Expedito Parente Jr,
Fortaleza, Brazil for helpful discussions.
Notes and references
1H NMR (400 MHz, DMSO-d6): Isomer 1, 9a (trans) d ¼ 5.74
(s, 1H, 2-H), 4.86 (t, J ¼ 5.6 Hz, 1H, OH), 4.21 (dddd, J ¼ 5.3,
5.3 Hz, 5.4 Hz, 6.8 Hz, 1H, 4-H), 4.00 (app. quint, J ¼ 7.4 Hz, 1H,
5-H), 3.69 (dd, J ¼ 5.4 Hz, J ¼ 7.4 Hz, 1H, 5-H), 3.39 (app. t, J ¼
5.3, 5.6 Hz, 1H, CH2OH), 3.39 (app. t, J ¼ 5.3, 5.6 Hz, 1H,
CH2OH), 3.17 (s, 3H, OCH3). Isomer 2, 9b (cis) d ¼ 5.73 (s, 1H, 2-
H), 4.85 (t, J ¼ 5.6 Hz, 1H, OH), 4.05–4.12 (m, 1H, 4-H), 4.00
(app. quint, J ¼ 7.4 Hz, 1H, 5-H), 3.65 (app. t, J ¼ 7.4 Hz, 1H, 5-
H), 3.53 (app. quint, J ¼ 5.6 Hz, 1H, CH2OH), 3.45 (app. quint, J
¼ 5.6 Hz, 1H, CH2OH), 3.18 (s, 3H, OCH3). 13C{1H} NMR (100
MHz, DMSO-d6): Isomer 1, 9a (trans) d ¼ 115.4 (C-2), 75.8 (C-4),
65.7 (C-5), 62.4 (CH2OH), 50.4 (OCH3). Isomer 2, 9b (cis) d ¼
115.2 (C-2), 76.7 (C-4), 65.3 (C-5), 61.5 (CH2OH), 50.4 (OCH3). IR:
3469, 2942, 2839, 1447, 1370, 1205, 1136, 1077, 1031, 984, 921,
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835 cmꢂ1
.
The peak assignment was done with the help of HSQC and
H,H-COSY spectra.
HRMS (ESI-TOF): m/z [M + Na]+ calcd C5H10O4: 157.04713;
found: 157.04717.
Synthesis of the allyl alcohol 11 from the orthoesters 9
A slurry of the crude orthoesters 9 (36.5 g), containing the pyr-
idinium p-toluenesulfonate from the rst step, was heated to
270 ꢀC at atmospheric pressure in a distillation apparatus. The
rst fraction was MeOH (62 ꢀC/atmospheric pressure), and aer
ꢀ
45 min the allyl alcohol (64–140 C/atmospheric pressure) was
immediately produced under the release of CO2. The slightly
yellow crude product, which nearly contains just the allyl
alcohol, was puried by distillation. Because allyl alcohol will
9 (a) G. Crank and F. W. Eastwood, Aust. J. Chem., 1964, 17,
1392–1398; (b) J. S. Josan and F. W. Eastwood, Carbohydr.
Res., 1968, 7, 161–166.
rapidly polymerize at temperatures above 45 ꢀC, it was removed 10 See also: (a) P. Camps, J. Cardellach, J. Font, R. M. Ortuno
˜
from the reaction mixture at room temperature in vacuo (0.5
mbar), whereby the product fractions where cooled with liquid
nitrogen. Finally, to remove traces of MeOH, the allyl alcohol
was concentrated at room temperature and 120 mbar for
30 min, yielding 11.9 g (76%) of allyl alcohol (11) as a colorless
and O. Ponsati, Tetrahedron, 1982, 38, 2395–2402; (b)
S. Hanessian, A. Bargiotti and M. LaRue, Tetrahedron Lett.,
1978, 19, 737–740; (c) E. Block, in Olen Synthesis by
Deoxygenation of Vicinal Diols, ed. W. G. Dauben, John
Wiley & Sons, New York, 1984, vol. 30, pp. 457–566.
liquid. 1H NMR (400 MHz, CDCl3): d ¼ 5.94 (ddt, J ¼ 5.1, 11 Reaction of glycerol and triethyl orthoformate at 100 ꢀC
10.4 Hz, 17.2 Hz, 1H, 2-H), 5.23 (app. dq, J ¼ 1.7, 17.2 Hz, 1H, 3-
Ha), 5.09 (app. dq, J ¼ 1.5, 10.4 Hz, 1H, 3-Hb), 4.08 (app. dt, J ¼
1.6, 5.1 Hz, 2H, 1-H). 13C{1H} NMR (100 MHz, CDCl3): d ¼ 137.2
(C-2), 115.0 (C-3), 63.6 (C-1).
without a catalyst gives a mixture of the 5- and 6-
membered orthoesters in a ratio of 76 : 24: Y. Yokoyama,
A. B. Padias, F. De Blauwe and H. K. Hall, Macromolecules,
1980, 13, 252–261.
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