Generalization of Concerted Nucleophilic Aromatic Substitution

• Project/Area Number: 17K19121
• Research Category: Grant-in-Aid for Challenging Research (Exploratory)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry and related fields
• Research Institution: Osaka University
• Principal Investigator: TOBISU Mamoru 大阪大学, 工学研究科, 教授 (60403143)
• Project Period (FY): 2017-06-30 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000); Fiscal Year 2018: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000); Fiscal Year 2017: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
• Keywords: 芳香族求核置換反応 / フェノール / 芳香族求核置換 / 協奏的芳香族求核置換反応

Outline of Final Research Achievements

The purpose of this study is the development of new concerted nucleophilic aromatic substitution reactions. To achieve this goal, we initially examine the synthesis of an imidazolium salt bearing a perfluorophenyl group at the 2-position. However, a mixture of 1:1 and 1:2 adducts were obtained. Another molecule examined in this study is a naphthalene bearing two dimesitylboryl group at the 1,8 positions, the structure of which was unambiguously determined by X-ray crystallography. Although this molecule was inert toward phenol derivatives under thermal conditions, photophysical and redox measurements suggest the potential reactivity under photochemical conditions.

Academic Significance and Societal Importance of the Research Achievements

ベンゼンに代表される芳香族化合物は代表的な有機化合物であり、その反応性は古くから研究されており、教科書でも扱われている。一般に求核剤と呼ばれる電子を豊富に持つ試薬との反応は、芳香族化合物では起こりにくく、強力な電子求引基を持つ場合にのみ起こるとされてきた。より一般性の高い求核剤との反応が最近数例報告されたものの、その反応の理解は進んでいない。そこで本研究では、その新しい芳香族化合物の反応形式が実現するための要因を明らかにし、有用物質合成への応用の可能性を検討した。