Ring-opening cyclization of spirocyclopropanes with ylide nucleophiles for the construction of carbocycles

2023 Fiscal Year Final Research Report

• Project/Area Number: 21K05048
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Kyoto Pharmaceutical University (2022-2023); University of Toyama (2021)
• Principal Investigator: NAMBU Hisanori 京都薬科大学, 薬学部, 教授 (80399956)
• Project Period (FY): 2021-04-01 – 2024-03-31
• Keywords: イリド反応剤 / スピロシクロプロパン / 炭素環 / リンイリド / 硫黄イリド / インダン / アズレン / スピロシクロブタン

Outline of Final Research Achievements

Ylide species, such as phosphorus ylides or sulfur ylides, have both a nucleophilic and an electrophilic moieties, These reagents have long been used as reagents in synthetic reactions to construct various building blocks. Although many examples of the construction of various heterocyclic compounds using the ring-opening cyclization reaction of cyclopropanes have been reported, there have been few examples of the construction of carbcyclic compounds, especially no examples of bicyclic carbocycles. Based on these backgrounds, we investigated the construction of carbocyclic systems by ring-opening cyclization of spirocyclopropanes using phosphorus ylides or sulfur ylides as carbon nucleophiles. We succeeded in developing new synthetic methods for the bicyclic compounds, indane and azulene, which are used as pharmaceutical compounds and organic materials. In addition, we also developed a new synthetic method for spirocyclobutane by ring-expansion reaction of spirocyclopropanes.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

学術的意義として、これまでに例のないイリド求核種とシクロプロパンとの反応を開発することに成功した。本研究では、高い反応性を示すスピロ型のシクロプロパンを用いることで、炭素求核種であるリンイリドや硫黄イリドとの反応が進行し、炭素環を構築できることを見出した。
社会的意義として，これらの合成法により得られる炭素環化合物であるインダン、アズレンおよびシクロブタンは医薬品や有機材料に用いられている骨格であることから、本合成法は医薬品や有機材料の開発研究の進展に貢献できる。