Angewandte Chemie International Edition in English

Volume 19, Issue 2 pp. 134-135

Communication

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Stereocontrolled Intramolecular Diels-Alder Reaction of Heterodienes; Studies on the Synthesis of Cannabinoids^†

Prof. Dr. Lutz-F. Tietze,

Prof. Dr. Lutz-F. Tietze

Organisch-chemisches Institut der Universität, Tammannstrasse 2, D-3400 Göttingen (Germany)

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Dipl.-Chem. Günter von Kiedrowski,

Dipl.-Chem. Günter von Kiedrowski

Organisch-chemisches Institut der Universität, Tammannstrasse 2, D-3400 Göttingen (Germany)

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Klaus Harms,

Klaus Harms

Anorganisch-chemisches Institut der Universität, Tammannstrasse 4, D-3400 Göttingen (Germany)

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Dr. William Clegg,

Dr. William Clegg

Anorganisch-chemisches Institut der Universität, Tammannstrasse 4, D-3400 Göttingen (Germany)

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Prof. Dr. George Sheldrick,

Corresponding Author

Prof. Dr. George Sheldrick

Anorganisch-chemisches Institut der Universität, Tammannstrasse 4, D-3400 Göttingen (Germany)

Anorganisch-chemisches Institut der Universität, Tammannstrasse 4, D-3400 Göttingen (Germany)Search for more papers by this author

Prof. Dr. Lutz-F. Tietze,

Prof. Dr. Lutz-F. Tietze

Organisch-chemisches Institut der Universität, Tammannstrasse 2, D-3400 Göttingen (Germany)

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Dipl.-Chem. Günter von Kiedrowski,

Dipl.-Chem. Günter von Kiedrowski

Organisch-chemisches Institut der Universität, Tammannstrasse 2, D-3400 Göttingen (Germany)

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Klaus Harms,

Klaus Harms

Anorganisch-chemisches Institut der Universität, Tammannstrasse 4, D-3400 Göttingen (Germany)

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Dr. William Clegg,

Dr. William Clegg

Anorganisch-chemisches Institut der Universität, Tammannstrasse 4, D-3400 Göttingen (Germany)

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Prof. Dr. George Sheldrick,

Corresponding Author

Prof. Dr. George Sheldrick

Anorganisch-chemisches Institut der Universität, Tammannstrasse 4, D-3400 Göttingen (Germany)

Anorganisch-chemisches Institut der Universität, Tammannstrasse 4, D-3400 Göttingen (Germany)Search for more papers by this author

First published: February 1980

https://doi.org/10.1002/anie.198001341

Citations: 55

^†

This work was supported by the Fonds der Chemischen Industrie. We wish to thank Prof. Dr. D. Leibfritz and Dr. M. Feigl, Universität Bremen, for recording the 360-MHz ¹H-NMR spectrum and the Dragoco Company, Holzminden, for supplying citronellal.

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The skeleton (4) of tetrahydrocannabinol having translinked rings A and B can be obtained optically pure from the diketone (1) and (R)-citronellal (2). The key step is intramolecular Diels-Alder reaction (up to 20°C!) of the heterodiene intermediate (3).—Derivatives of (4) are of interest, e.g., in the treatment of glaucoma.

References

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8 The 100-MHz ¹H-NMR spectrum does not provide information about the configuration of the centers of chirality in (4)—¹H-NMR (360 MHz, CDCl₃); δ = 2.79 (ddt, J_10α.10β = 11.5 Hz, J_10α.9 = J_10α.10a = 3.0 Hz, J_10α.8β J = 1.7 Hz, 10α-H), 2.43—2.16 (m, 2α, 2β, 4α, 4β-H), 2.09 (tdd, J_10a.10β = J_10a.6a = 11.5 Hz, J_10a.10α = 3.0 Hz, J_10a.4α = 2.0 Hz, 10a-H), 1.94—1.84 (m, 3α, 3β-H), 1.84—1.76 (m, 8α-H) 1.76—1.70 (m, 7β-H), 1.60—1.50 (m, 9-H), 1.33 (s, 6-CH₃), 1.26 (dt, J_7α = J_6a.10a = 11.5 Hz, J_6a.7β = 2.5 Hz, 6a-H), 1.04 (s, 6-CH₃), 0.94—1.13 (m, 7α, 8β-H), 0.90 (d, J = 6.5 Hz, 9-CH₃), 0.49 (q, J_10β.10α = J_10β.9 = J_10β.9 = 11.5 Hz, 10β-H).
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9 X-ray structure analysis was performed on (±)-(4), prepared from (±)-citronellal and (1). The absolute configuration of (4) follows from the chirality in reactant (2).—We have deposited the atomic coordinates and other crystallographic data at the Cambridge Data Centre (England).
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Volume19, Issue2

February 1980

Pages 134-135

Stereocontrolled Intramolecular Diels-Alder Reaction of Heterodienes; Studies on the Synthesis of Cannabinoids^†

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Stereocontrolled Intramolecular Diels-Alder Reaction of Heterodienes; Studies on the Synthesis of Cannabinoids^†