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DOI: 10.1055/s-2007-985598
Stereoselective Synthesis of (3S,8R,9R,10R)-Heptadeca-1-ene-4,6-diyne Tetrol and Its 3-Epimer from d-Mannitol [1]
Publication History
Publication Date:
22 August 2007 (online)
![](https://www.thieme-connect.de/media/synlett/200715/lookinside/thumbnails/10.1055-s-2007-985598-1.jpg)
Abstract
(3S,8R,9R,10R)-Heptadeca-1-ene-4,6-diyne tetrol and its 3-epimer were synthesized, and it was found that the relative configuration which was proposed for 1 was incorrect.
Key words
polyacetylene - Cadiot-Chodkiewicz cross-coupling reaction - Th2-type diseases - d-mannitol
IICT Communication No. 070414.
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8a
Spectral data of 5: [α]D 30 +57.3 (c = 2.97, CHCl3). 1H NMR (600 MHz, CDCl3): δ = 4.78 (d, J = 7.1 Hz, 1 H), 4.70 (d, J = 7.1 Hz, 1 H), 4.60 (d, J = 7.1 Hz, 1 H), 4.08 (dd, J = 4.3, 7.1 Hz, 1 H), 3.75 (dt, J = 4.3, 5.8 Hz, 1 H), 3.65-3.71 (m, 2 H), 3.49-3.50 (m, 2 H), 3.33 (s, 3 H), 1.45-1.50 (m, 2 H), 1.40 (s, 3 H), 1.32 (s, 3 H), 1.18-1.24 (m, 10 H), 0.8 (t, J = 6.7 Hz, 3 H). 13C NMR (150 MHz, CDCl3): δ = 110.2, 95.5, 83.1, 78.1, 75.9, 71.6, 67.1, 66.9, 58.9, 46.6, 31.7, 31.4, 29.5, 29.1, 26.5, 25.6, 25.2, 22.5, 14.0.
MS (LCMS): m/z = 443 [M(79Br) + Na]+, 445 [M(81Br) + Na]+. -
8b
Spectral data of 4a: [α]D 30 -45.3 (c = 2.28, CHCl3). 1H NMR (200 MHz, CDCl3): δ = 7.30-7.86 (m, 10 H), 5.87 (ddd, J = 5.1, 10.2, 16.8 Hz, 1 H), 5.29 (dt, J = 1.4, 16.8 Hz, 1 H), 5.11 (dt, J = 1.4, 10.2 Hz, 1 H), 4.80 (m, 1 H), 2.37 (d, J = 2.2 Hz, 1 H), 1.10 (s, 9 H). 13C NMR (150 MHz, CDCl3): δ = 137.0, 135.9, 135.8, 133.2, 133.1, 129.8, 127.5, 127.4, 115.6, 83.0, 73.8, 64.3, 26.8, 19.3. MS (LCMS): m/z = 343 [M + Na]+, 279 [M - 64 + Na]+.
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8c
Spectral data of 1a: [α]D 32 +6.0 (c = 0.20, MeOH). 1H NMR (300 MHz, CDCl3): δ = 5.94 (ddd, J = 5.2, 10.2, 16.6 Hz, 1 H), 5.47 (d, J = 16.6 Hz, 1 H), 5.27 (d, J = 10.2 Hz, 1 H), 4.94 (d, J = 5.2 Hz, 1 H), 4.68 (d, J = 3.7 Hz, 1 H), 3.81 (ddd, J = 4.0, 4.5, 8.3 Hz, 1 H), 3.60 (dd, J = 3.7, 4.5 Hz, 1 H), 1.43-1.65 (m, 2 H), 1.06-1.32 (br m, 10 H), 0.88 (br t, J = 6.8 Hz, 3 H). 13C NMR (150 MHz, CDCl3): δ = 135.6, 117.4, 78.4, 78.3, 75.6, 72.7, 70.1, 70.0, 63.8, 63.4, 33.1, 31.7, 29.5, 29.2, 25.5, 22.6, 14.0. MS (LCMS): m/z = 317 [M + Na]+.
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12a
Spectral data of 4b: [α]D 30 +45.6 (c = 2.90, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 7.30-7.86 (m, 10 H), 5.91 (ddd, J = 5.2, 10.1, 17.1 Hz, 1 H), 5.33 (dt, J = 1.3, 17.1 Hz, 1 H), 5.13 (dt, J = 1.3, 10.1 Hz, 1 H), 4.83-4.85 (m, 1 H), 2.44 (d, J = 2.3 Hz, 1 H), 1.11 (s, 9 H). 13C NMR (150 MHz, CDCl3): δ = 137.0, 135.9, 135.8, 133.2, 133.1, 129.7, 127.5, 127.4, 115.6, 83.0, 73.8, 64.3, 26.8, 19.3. MS (LCMS): m/z = 343 [M + Na]+, 279 [M - 64 + Na]+.
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12b
Spectral data of 1b: [α]D 32 -20.92 (c = 0.65, MeOH). 1H NMR (300 MHz, CDCl3): δ = 5.93 (ddd, J = 5.3, 10.2, 17.0 Hz, 1 H), 5.47 (d, J = 17.0 Hz, 1 H), 5.25 (d, J = 10.2 Hz, 1 H), 4.93 (d, J = 5.3 Hz, 1 H), 4.66 (d, J = 3.5 Hz, 1 H), 3.80 (ddd, J = 3.5, 4.5, 8.1 Hz, 1 H), 3.63 (dd, J = 3.5, 4.5 Hz, 1 H), 1.44-1.63 (m, 2 H), 1.20-1.36 (br m, 10 H), 0.88 (br t, J = 6.98 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 135.7, 117.2, 78.4, 77.1, 75.9, 72.5, 70.1, 70.0, 63.6, 63.1, 32.7, 31.8, 29.5, 29.2, 25.6, 22.6, 14.0. MS (LCMS): m/z = 317 [M + Na]+.
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References and Notes
IICT Communication No. 070414.