| Project/Area Number |
03453152
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Chemical pharmacy
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| Research Institution | TOHOKU UNIVERSITY |
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Principal Investigator |
TAKANO Seiichi Tohoku University, Pharmaceutical Institute, Professor, 薬学部, 教授 (20004559)
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| Co-Investigator(Kenkyū-buntansha) |
SUGAHARA Tsutomu Tohoku University, Pharmaceutical Institute, Research Associate, 薬学部, 助手 (50006350)
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| Project Period (FY) |
1991 – 1993
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| Project Status |
Completed (Fiscal Year 1993)
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| Budget Amount *help |
¥6,700,000 (Direct Cost: ¥6,700,000)
Fiscal Year 1993: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1992: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1991: ¥4,400,000 (Direct Cost: ¥4,400,000)
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| Keywords | Chiral building block / Chiral cyclopentadienone synthon / Chiral cyclohexadienone synthon / Chiral bicyclo[2.2.1]heptane system / Lipase-mediated resolution / Enantiomerization / Asymmetrization of mesomer / Retro-Diels-Alder Cleavage / キラルシクロペンタジエノン素子 / キラルシクロヘキサジエノン素子 / リパーゼ / メソ型対称性 / パラジウム触媒 / マンガン(III)アセテート / 二酸化セレン / ケトージシクロペンタジエン / エナンチオ制御合成 / フィシャーインドール化反応 / ディールス・アルダー反応 / ベータキュパレノン / ヘルベルテン / アプリシン / エストロン / エナンチオメリゼ-ション / ジシクロペンタジエノ-ル / リパ-ゼ / 不斉アシル化 / キネチック分割 / フィゾスチグミン / アファノルフィン |
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| Research Abstract |
Two chiral building blocks having bicyclo[2.2.1]heptane ring system have been prepared by employing lipase mediated resolution as the key step. Namely, optically pure ketodicyclopentadiene serving as chiral equivalent of cyclopentadienone was prepared from dicyclopentadiene by empoying either lipase mediated asymmetric esterification or deacylation reaction. An efficient procedure for the enantiomerization has also been established. On the other hand, optically pure homoketodicyclopentadiene serving as chiral equivalent of cyclohexadienone was prepared in both enatiomeric forms from the Diels-Alder adduct of p-benzoquinone and cyclopentadiene by asymmetrization via the lipase-mediated enantiospecific mono-esterification of the meso-symmetric intermediate.
Based on molecular bias of these componds owing to the bicyclo[2.2.1]heptane ring system and facile retro-Diels-Alder removal of cyclopentadiene, a variety of physiologically active natural products ranging from a simple monoterpene to a complex polyoxygenated plant toxin have been synthesized in a complete stereocontrolled way.
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