Synthetic Studies on Aphidicolane and Stemodane Diterpenes. V. A Facile Formal Total Synthesis of (±)-Aphidicolin via a Lewis Acid-Mediated Stereoselective Spiroannelation

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概要

• 論文の詳細を見る

• Formal total synthesis of (±)-aphidicolin (1) was achieved via a Lewis acid-mediated stereoselective spiroannelation reaction as a key step. The bisbenzyl acetal (2) was synthesized from the readily available dimethyl acetal (4). Treatment of 2 with trimethylsilyl trifluoromethanesulfonate (TMSOTf) afforded a 69 : 31 mixture of the spirocyclic enones (9 and 10) in excellent yield. The tricyclic ketal-ketone (3) corresponding to the B/C/D rings of 1 was easily generated from the enone (9) by intramolecular alkylation and catalytic hydrogenation as principal steps. The A-ring construction was performed by a procedure similar to one used previously. Barbier reaction of 14,followed by oxidative rearrangement, stereoselective 1,4-addition of a methyl group, and subsequent intramolecular aldol-condensation afforded the tetracyclic enone (18), which has already been transformed into (±)-aphidicolin (1).

• 社団法人日本薬学会の論文
• 1995-08-15

著者

• 金 相元

  Faculty of Pharmaceutical Sciences, Josai University

• 田中 徹明

  Faculty of Pharmaceutical Sciences, Osaka University

• 村上 和夫

  Faculty of Pharmaceutical Sciences, Osaka University

• 奥田 修

  Faculty of Pharmaceutical Sciences, Osaka University

• 吉野 仁

  Faculty of Pharmaceutical Sciences, Osaka University

• 岩田 宙造

  Faculty of Pharmaceutical Sciences, Osaka University

• 村上 和夫

  阪大院薬

• 金 相元

  Faculty Of Pharmaceutical Sciences Josai University

• 吉野 仁

  阪大院薬

• 岩田 宙造

  阪大院薬

• 田中 徹明

  阪大院薬

• 田中 徹明

  Faculty Of Pharmaceutical Sciences Osaka University

• Tanaka T

  Kvushu Univ. Fukuoka Jpn

• 三神山 秀勲

  阪大薬

• 三神山 秀勲

  Faculty of Pharmaceutical Sciences, Osaka University

• 神田 篤

  Faculty of Pharmaceutical Sciences, Osaka University

• Tanaka T

  Osaka Univ. Osaka Jpn

• Kim S‐w

  Faculty Of Pharmaceutical Sciences Josai University

• 岩田 宙造

  Faculty Of Pharmaceutical Sciences Osaka University

• 神田 篤

  Faculty Of Pharmaceutical Sciences Osaka University

• Kanda Atsushi

  Faculty Of Pharmaceutical Sciences Osaka University

• 田中 恒雄

  Department Of Pharmacy Hyogo College Of Medicine

• Tanaka Tetsuaki

  Faculty Of Pharmaceutical Sciences Osaka University

• Yamashita Haruhisa

  Faculty Of Pharmaceutical Sciences Kanazawa University

• 吉野 仁

  Faculty Of Pharmaceutical Sciences Osaka University

• Okuda O

  Faculty Of Pharmaceutical Sciences Toyama Medical And Pharmaceutical University

• 奥田 修

  Faculty Of Pharmaceutical Sciences Osaka University

• Murakami K

  Osaka Univ. Osaka Jpn

• Murakami K

  阪大院薬

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