Total Synthesis of (-)-Gephylotoxin 223AB via Asymmetric 1,3-Dipolar Cycloaddition

• Project/Area Number: 62570953
• Research Category: Grant-in-Aid for General Scientific Research (C)
• Allocation Type: Single-year Grants
• Research Field: Chemical pharmacy
• Research Institution: Tokyo College of Pharmacy
• Principal Investigator: KIBAYASHI Chihiro Tokyo College of Pharmacy, 薬学部, 教授 (80057330)
• Project Period (FY): 1987 – 1988
• Project Status: Completed (Fiscal Year 1988)
• Budget Amount: ¥1,900,000 (Direct Cost: ¥1,900,000); Fiscal Year 1988: ¥300,000 (Direct Cost: ¥300,000); Fiscal Year 1987: ¥1,600,000 (Direct Cost: ¥1,600,000)
• Keywords: Asymmetric 1,3-Dipolar Cycloaddition / Nitrone / (S)-Allyl Ether / Inside Alkoxy Transition State / (-)-Coniine / (+) -モノモリン I / 不斉1,3ー双極子環付加反応 / (+)-モノモリン I

Research Abstract

Asymmetric 1,3-dipolar cycloaddition of nitrones by using a chiral allyl ether as a dipolarophile and application to an enantioselective synthesis of (-)-coniine and (+)-monomorine I has been investigated. The cyclic and acyclic nitrones were allowed to react with (s)-3-benzyloxy-1-heptene, resulting in the preferential formation (3:1) of the (2R,3aS)-and (3S,5R)-isoxazolidine derivatives, respectively, predicted by application of the inside alkoxy more reactive conformation in a transition state. These cycloadducts were enantiomerically converted to (-)-coniine and (+)-monomorine I,respectively.

Research Products

• [Publications] 伊藤昌之、樹林千尋: J.Am.Chem.Soc.
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Masayuki Ito; Chihiro Kibayashi: "Asymmetric Induction in Nitrone Cycloaddition with a Chiral Allyl Ether. Enantioselective Synthesis of (-)-Coniine and (+)-Monomorine I" J. Am. Chem. Soc.,Submitted.
  • Description: 「研究成果報告書概要(欧文)」より