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A steroselective synthesis of (22R, 23R)-methylenecholesterol

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Abstract

The marine sterol (22R, 23R)-methylenecholesterol1 has been synthesized from readily available C-22 steroidal ester2 utilizing an intermolecular acyclic ester enolate alkylation as the key step.

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Literature Cited

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    Blanc, P., Djerassi, C.:J. Am. Chem. Soc.,102, 7113 (1980); (b) Lang, R. W., Djerassi, C.:J. Org. Chem.,47, 625 (1982); (c) Anderson, G. D., Powers, T.J., Djerassi, C., Fayos, J., Clardy, J.:J. Am. Chem. Soc.,97, 388 (1975).

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    All compounds gave satisfactory IR,1H and13C NMR spectral data. Compounds4: IR (film) 1731 cm−1;1H NMR (300 MHz, CDCl3) δ 5.80 (m, 1H), 5.01 (m, 2H), 4.12 (q,J=7.2 Hz, 2H), 3.33 (s, 3H), 2.77 (br t, 1H), 1.02 (s, 3H), 0.75 (s, 3H), 0.67–0.64 (m, 1H), 0.46–0.43 (m, 1H);13NMR (20 MHz, CDCl3) δ 178.5, 137.4, 115.4, 82.1, 59.9, 56.6, 56.5, 53.7, 48.3, 48.0, 43.3, 42.8, 40.3, 37.8, 35.2, 35.0, 33.3, 30.5, 28.4, 28.0, 24.9, 24.0, 22.7, 21.4, 19.1, 14.6, 14.2, 13.0, 12.2. Compound5:1H NMR (300 MHz, CDCl3) δ 5.76 (m, 1H), 5.05 (m, 2H), 4.17 (dd,J=9.6, 4.8 Hz, 1H), 4.05 (t,J=9.4, 1H), 3.32 (s, 3H), 2.99 (s, 3H), 2.77 (br t, 1H), 1.02 (s, 3H), 0.74 (s, 3H), 0.66–0.63 (m, 1H), 0.45–0.41 (m, 1H);13C NMR (75 MHz, CDCl3) δ 136.8, 116.7, 82.3, 71.0, 56.5, 56.4, 53.1, 48.0, 43.3, 42.8, 40.3, 39.9, 37.2, 35.3, 35.0, 34.9, 33.3, 30.5, 29.6, 28.0, 24.9, 24.0, 22.8, 21.5, 19.2, 13.2, 13.0, 12.2. Compound 7: IR (film) 1715 cm−1;1H NMR (300 MHz, CDCl3) δ 8.98 (d,J=5.62 Hz, 1H), 3.32 (s, 3H), 2.77 (t,J=2.7 Hz, 1H), 1.01 (s, 3H), 0.67 (s, 3H), 0.45–0.42 (m, 1H);13C NMR (75 MHz, CDCl3) δ 201.3, 82.3, 57.4, 56.5, 56.2, 48.0, 43.4, 43.0, 40.0, 39.3, 35.2, 35.1, 33.3, 30.6, 30.5, 28.8, 27.9, 24.9, 24.1, 22.7, 21.4, 19.5, 19.2, 16.8, 13.1, 12.3. Compound8:1H NMR (200 MHz, CDCl3) δ 4.55 (d,J=13.8 Hz, 1H). 3.32 (s, 3H), 2.77 (t,J=4.0 Hz, 1H), 1.72 (s, 3H), 1.67 (s, 3H), 1.02 (s, 3H), 0.67 (S, 3H), 0.49–0.45 (m, 3H). Compound9:1H NMR (80 MHz, CDCl3) δ 3.32 (s, 3H), 2.77 (br t, 1H), 1.01 (s, 3H), 0.99 (d,J=6.7 Hz, 3H), 0.90 (t,J=6.7 Hz, 6H), 0.66 (s, 3H), 0.45–0.38 (m, 4H), 0.22–0.18 (m, 3H).

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    Ishiguro, M., Akaiwa, A., Fujimoto, Y., Sato, S., Ikekawa, N.:Tetrahedron Lett., 763 (1979). (b) Sato, S., Akaiwa, A., Fujimoto, Y., Ishiguro, M., Ikekawa, N.:Chem. Pharm. Bull.,29, 406 (1981).

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    We are grateful to Professor C. Djerassi (Stanford University) for providing us with reference spectra for 1.

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Correspondence to Deukjoon Kim.

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Kim, D. A steroselective synthesis of (22R, 23R)-methylenecholesterol. Arch. Pharm. Res. 15, 374–375 (1992). https://doi.org/10.1007/BF02974116

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Keywords

  • Synthesis
  • marine sterol, (22R, 23R)-methylenecholesterol
  • intermolecular acyclic ester enolate alkylation