ドナー・アクセプター置換シクロプロパンの環開裂を伴う分子内環化と分子間付加：S<sub>N</sub>1およびS<sub>N</sub>2機構を利用する高立体選択的合成

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  • 西井 良典
    信州大学繊維学部化学材料学科応用分子科学コース

書誌事項

タイトル別名
  • Highly Stereoselective Synthesis Using Donor-Acceptor Cyclopropanes via S<sub>N</sub>1 or S<sub>N</sub>2 Mechanism on the Occasion of Cyclopropane Ring-opening
  • ドナー・アクセプター置換シクロプロパンの環開裂を伴う分子内環化と分子間付加 : S[N]1およびS[N]2機構を利用する高立体選択的合成
  • ドナー ・ アクセプター チカン シクロプロパン ノ カンカイレツ オ トモナウ ブンシ ナイカンカ ト ブンシ カン フカ : S[N]1 オヨビ S[N]2 キコウ オ リヨウ スル コウリッタイ センタクテキ ゴウセイ

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説明

<p>Cyclopropanes represent an important class of organic compounds due to their synthetic utility and their widespread occurrence in nature. In addition, the rigid conformation of cyclopropanes as the smallest conceivable [C3] ring compound can be exploited in stereo-controlled syntheses. Especially donor-acceptor (D-A) cyclopropanes have attracted considerable attention due to recent synthetic developments. This article describes the ring-opening cyclization, homo-Nazarov cyclization, oxy-homo-Michael reaction, 1,5-addition and reductive ring-opening reaction of enantioenriched donor-acceptor cyclopropanes. In addition, a couple of asymmetric total synthesis of bioactive lignans using a couple of these reactions as key steps. Namely, we achieved the asymmetric total synthesis of tupichilignan A using the highly stereoselective Cu(OTf)2-catalyzed oxy-homo-Michael (OHM) addition of alcohols into bicyclic donor-acceptor cyclopropanes as a key step. Moreover, Cu-catalyzed 1,5-addtion of Grignard reagent instead of alcohols into the enantioenriched donor-acceptor cyclopropanes also proceeded with high regio- and stereoselectivity. In addition, we reported the hydrogenolysis (reductive ring-opening) of D-A cyclopropanes and its application for the total synthesis of yatein. Beside the intermolecular reaction, we verify the reaction mechanism of ring-opening cyclization and homo-Nazarov cyclization of D-A cyclopropanes. Based on the mechanistic point, this paper describes the highly stereoselective synthetic methods utilizing (i) the intermolecular addition of nucleophiles to enantioenriched D-A cyclopropanes via SN2 pathway and (ii) the intramolecular chiral transfer Friedel-Crafts alkylation via SN1 pathway after cyclopropane-opening.</p>

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