23 EudesmanolideからEthanoadamantanoneへの転位反応と中間体の構造

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概要

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• A novel cyclization-skeletal rearrangement a eudesmanolide, 3-deoxy-4β,5αH-hexahydro-l-α-santonin (1) to an ethanoadamanone, (-)-2,5,9-trimethyltetracyclo[6.3.1.0^<2,6>.0^<5,9>]dodecan-11-one (2) was found in a most unusual reaction of 1 with. hot phosphoryl chloride. Two new tricyclic ketones as the possible intermediates were isolated in the aforementioned reaction. The structure, conformation and absolute configuration of the crystalline ketone was determined mainly on the basis of the X-ray crystallograpic analysis and CD/ORD spectrometry. The structure thus revealed is (+)-1β,3α,6αH,4α,7β,11-trimethyltricyclo[5.4.1^<3,6>.0^<1,7>]dodec-10-en-5-one (3). The structure of the other oily ketone, (+)-4αH,3α,7β,11-trimetyltricyclo[5.4.1^<1,4>.0^<1,7>]dodec-10-en-2-one (4) was deduced from the absolute structure of its crystalline 10α,11α-epoxide (5), which was also established by the same methods as described above. Tricycloeudesmenones (3 and 4) can be regarded as a pair of ring analogs of the cyclopentanone (C) situated on the cyclohexane (B) of the same non-steroid type cis-fused octalin (A/B). A possible reaction pathway for 3 and 4 formed by cyclization from santanolide (1) was proposed. The proposed skeletal rearrangement pathway to ethanoadamantanone (2), starting from the tetracyclic ketone (B) derived from 3 via a tricyclic intermediate (A), was performed through a hypothetical pathway involving intermediates (C and D) by the use of a computer technique for the bond migration by 1,2-shift.

• 天然有機化合物討論会の論文
• 1979-09-20

著者

• 飯高 洋一

  東大・薬

• 飯高 洋一

  Nishi-tokyo Science University

• 柴田 徹一

  慶應義塾大学薬化学研究所

• 飯高 洋一

  Faculty Of Pharmaceutical Sciences University Of Tokyo

• 飯高 洋一

  西東京科学大学理工学部

• 廣瀬 忠明

  慶大医

• 川又 健

  Pharmaceutical Institute, School of Medicine, Keio University

• 稲山 誠一

  慶大・医

• 川又 健

  慶大・医

• 柴田 徹一

  慶大・医

• 大坂 哲司

  Pharmaceutical Institute, School of Medicine, Keio University

• 稲山 誠一

  Institute Of Oriental Medical Sciences

• 稲山 誠一

  慶應義塾大学医学部薬化学研究所

• シン A.

  慶大・医

• 大坂 哲司

  慶大・医・薬化研

• 広瀬 忠明

  慶大・医

• 川又 健

  Pharmaceutical Institute School Of Medicine Keio University

• 大坂 哲司

  Pharmaceutical Institute School Of Medicine Keio University

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