Rapid and Easy Access to 1,3-Enynes, 1,3-Diynes and Allenes
(100), 95 (70), 55 (15). C13H24OSi (228.33): calcd. C 64.23, H 9.58;
found C 64.43, H 9.65.
caino is acknowledged for his technical support in recording the
MS spectra.
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(E)-1-Ethoxyoct-1-en-3-yne (5): Purified by flash chromatography
(Et2O/petroleum ether, 1:4, 1% Et3N, Rf = 0.58) to give 5 (204 mg,
67%). H NMR (200 MHz, CDCl3): δ = 6.73 (d, J = 12.81 Hz, 1
H), 4.89 (d, J = 12.81 Hz, 1 H), 3.76 (q, J = 7.03 Hz, 2 H), 2.26
(t, J = 2.20 Hz, 2 H), 1.52–1.41 (m, 4 H), 1.27 (t, J = 7.03 Hz, 3
H), 0.93–0.83 (t, J = 6.95 Hz, 3 H) ppm. 13C NMR (50.33 MHz,
CDCl3): δ = 156.2 (d), 88.1 (s), 85.7 (d), 75.8 (s), 65.3 (t), 30.9 (t),
21.8 (t), 18.9 (t), 14.4 (q), 13.4 (q) ppm. MS: m/z (%) = 152 (100)
[M]+, 109 (40), 95 (65), 75 (51), 57 (17). C13H24O3 (228.33): calcd.
C 68.38, H 10.59; found C 68.66, H 10.45.
1
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(E)-4-(Ethoxymethylene)-2,2-dimethyldec-5-yn-3-ol (6): Purified by
flash chromatography (Et2O/petroleum ether, 1:4, 1% Et3N, Rf =
0.48) to give 6 (168 mg, 75%). H NMR (200 MHz, CDCl3): δ =
1
6.36 (s, 1 H), 3.92 (q, J = 7.08 Hz, 2 H), 3.63–3.52 (d, J = 6.08 Hz,
1 H), 2.35 (t, J = 6.82 Hz, 2 H), 1.93 (d, J = 6.08 Hz, 1 H), 1.51–
1.30 (m, 4 H), 1.25 (t, J = 6.82 Hz, 3 H) 0.96 (s, 9 H) superimposed
on (t, J = 7.08 Hz, 3 H) ppm. 13C NMR (50.33 MHz, CDCl3): δ =
152.3 (d), 101.25 (s), 97.85 (s), 79.33 (d), 74.28 (s), 68.68 (t), 36.00
(s), 30.61 (t), 26.50 (q), 21.80 (t), 19.37 (t), 14.99 (q), 14.25 (q) ppm.
MS: m/z (%) = 238 (10) [M]+, 223 (100), 195 (45), 181 (5), 69 (5).
C15H26O2 (228.33): calcd. C 75.58, H 10.99; found C 75.66, H
10.75.
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4-(Diethoxymethyl)-2,2-dimethylnona-4,5-dien-3-ol (9): Purified by
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0.48) to give 9 as a mixture of diastereoisomers (306 mg, 54%). 1H
NMR (200 MHz, CDCl3): δ = 5.35 (t, J = 6.05 Hz, 1 H), 4.92 (s,
1 H), 3.92 (d, J = 4.04 Hz, 1 H), 3.73–3.45 (m, 4 H), 2.72 (d, J =
4.04 Hz, 1 H), 2.01 (m, 2 H), 1.85 (m, 4 H), 1.25 (t, J = 6.82 Hz,
6818.
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6 H), 0.93 (s, 9 H) superimposed on (t, J = 7.08 Hz, 3 H) ppm. 13
C
NMR (50.33 MHz, CDCl3): δ = 202.2 (s), 137.55 (s), 103.13 (d),
102.96 (d), 94.60 (d), 60.52 (t), 35.98 (s), 32.36 (t), 29.64 (t), 25.06
(q), 23.09 (t), 15.92 (q), 14.75 (q) ppm. MS: m/z (%) = 284 (10)
[M]+, 223 (100), 195 (45), 181 (5), 69 (5). C17H32O3 (284.44): calcd.
C 71.79, H 11.34; found C 71.66, H 11.45.
Supporting Information (see also the footnote on the first page of
this article): Experimental procedures and copies of the 1H and 13
C
NMR spectra of compounds 2a, 3a–f, 4a–d, 5, 6 and 9.
Acknowledgments
We thank thte Ministero dell’Università e della Ricerca (MIUR)
and the University of Turin for financial support. Dr. Roberto Bus-
Eur. J. Org. Chem. 2007, 5867–5874
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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