Stereoselective Synthesis of (3S,8R,9R,10R)-Heptadeca-1-ene-4,6-diyne Tetrol and Its 3-Epimer from d-Mannitol [1]

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

1

IICT Communication No. 070414.

References and Notes

• 2 Ramos F. Takaishi Y. Kawazoe K. Osorio C. Duque C. Acuña R. Fujimoto Y. Sato M. Okamoto M. Oshikawa T. Ahmed SU. Phytochemistry  2006,  67:  1143 
• 3 Cadiot PCR. Chodkiewicz W. In Chemistry of Acetylenes   Viehe HG. Marcel Dekker; New York: 1969.  p.597 
• 4 Wiggins L. J. Chem. Soc.  1946,  13 
• 5 Lipshutz BH. Sengupta S. Org. React. (N. Y.)  1992,  41:  135 
• 6 Corey EJ. Fuchs PL. Tetrahedron Lett.  1972,  13:  3769 
• 7 Hofmeister H. Annen K. Laurent H. Wiechert R. Angew. Chem., Int. Ed. Engl.  1984,  23:  727 
• 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]⁺.

• 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]⁺.

• 9 Lu W. Zheng G. Cai J. Synlett  1998,  737 
• 10 Yadav JS. Chander MC. Rao Srinivas C. Tetrahedron Lett.  1989,  30:  5455 
• 11 Garegg PG. Samuclson B. Synthesis  1979,  813 
• 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]⁺.

• 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]⁺.

• 13 Higashibayashi S. Czechtisky W. Kobayashi Y. Kishi Y. J. Am. Chem. Soc.  2003,  125:  14379 

1

IICT Communication No. 070414.