Mendeleev Commun., 2013, 23, 321–322
to apply tandem procedures ‘oxidation–elimination’ as a way to
Thus, we have developed a simple and practical procedure to
convert a commercially available lactone diol 1 into synthetically
attractive compound 2 in overall yield 82%.
product 2. Indeed, oxidation of compound 3 with Jones reagent
proceeded rapidly and led to mixture 2 + 5 inseparable by column
chromatography. Therefore, this mixture, without separation, was
treated with triethylamine in benzene for 8 h affording smoothly
the target cyclopentenone 2.††
This study was supported by the Ministry of Education and
Science of the Russian Federation (state contract no. 14.740.11.0367
)
and the President of the Republic of Bashkortostan (grant no. 5
of February 12, 2013).
§
4
-Chloromethyl-5-hydroxyhexahydro-2H-cyclopenta[b]furan-2-one 6.
A solution of 3 (0.2 g) in methanol (10 ml) was added to a 40% aqueous
solution of KOH (2 ml) and stirred at room temperature for 2 h, acidified
with 10% HCl to pH 2–3 and concentrated in vacuo. The residue was
extracted with ethyl acetate and dried (Na SO ). Concentration and puri-
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.mencom.2013.11.005.
2
4
fication by column chromatography (ethyl acetate–light petroleum, 1:3)
afforded 0.15 g (94%) of compound 6. Light yellow liquid, R = 0.6 (SiO ,
f
2
References
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2
1
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1
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8
1
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¶
Transformation of 3 into 1. 40% aqueous solution of KOH (2 ml) was
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2
Na SO . The extract was concentrated and purified by column chromato-
2
4
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3
identical with the authentic sample.
††
Methyl (5-methylidene-4-oxocyclopent-2-en-1-yl)acetate 2. To a solu-
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(
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i
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2
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extract containing the mixture 2 + 5 in 4:1 ratio (according to H NMR
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7
(
2
8 (a) H. Tanaka, T. Hasegawa, N. Kita, H. Nakahara, T. Shibata, S. Oe,
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(
0.3 g, 89%). Colourless liquid, R = 0.4 (SiO , 15% EtOAc in hexane).
f 2
1
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3
(
dd, 1H, J 6.4 and 16.2 Hz), 3.73 (s, 3H), 3.75–3.85 (m, 1H), 5.48 (s, 1H),
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6
6
1
1
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3
–1
44.4, 161.0, 171.7, 195.7. IR (neat, n/cm ): 2953, 1734, 1707, 1437, 1242,
+
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9
10
3
1
Methyl (5-chloromethyl-4-oxocyclopent-2-en-1-yl)acetate 5 (in a mix-
1
ture with 2): R = 0.4 (SiO , 15% EtOAc in hexane). H NMR (500 MHz,
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f
2
2
010, 21, 2794; (c) A. G. Martinez, E. T. Vilar, A. G. Fraile, S. M. Cerero,
3
S. O. Osuna and B. L. Marato, Tetrahedron Lett., 2001, 42, 7795.
3
.65–3.71 (m, 1H), 3.72 (s, 3H), 3.84–3.79 (m, 1H), 6.41 (dd, 1H, J 2.0
13
and 5.9 Hz), 7.71 (dd, 1H, J 2.4 and 5.7 Hz). C NMR (125 MHz, CDCl3)
d: 41.5, 43.3, 52.3, 117.7, 134.1, 144.4, 166.1, 171.7, 195.7.
Received: 10th July 2013; Com. 13/4156
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