Construction of Medium-sized Carbocycles Based on Pericyclic Reactions: Application to Natural Product Synthesis

2023 Fiscal Year Final Research Report

• Project/Area Number: 21H01923
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Hokkaido University
• Principal Investigator: Tanino Keiji 北海道大学, 理学研究院, 教授 (40217146)
• Project Period (FY): 2021-04-01 – 2024-03-31
• Keywords: ペリ環状反応 / 中員環 / 天然物 / 全合成 / 高次構造

Outline of Final Research Achievements

New methods for the construction of medium-sized carbocycles were developed based on pericyclic reactions. The 8pi-electrocyclic reaction of triene derivatives under basic conditions gave rise to seven-membered carbocycles. The utility of the new method was demonstrated through the concise total synthesis of 6,11-epoxyisodaucane, an essential oil constituent extracted from the Tritomaria polita liverwort.
On the other hand, the Cope rearrangement reaction of a five-membered gem-divinyl compound was developed for obtaining a nine-membered compound. The product was transformed into an analogue of Cristaxenicin A, a natural product having a unique core structure consisting of a nine-membered carbocycle coupled with a substituted dihydropyran.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

天然物の全合成研究は、新しい合成手法の開発を促し、有機化学の飛躍的な発展をもたらしてきた。その意義は学術面に留まらず、医薬や農薬の創出など社会的な要請にも応えるものである。
本研究では、新たに7から9員環までの大きさをもつ炭素環の効率的な構築法を開発し、それら新手法の有用性を天然物の全合成において検証した。合成標的の一つであるCristaxenicin Aは、リーシュマニア症の原因原虫に対する抗原虫活性を示し、治療薬のリード化合物として期待される天然物である。