Development of Direct Conversion Reactions of Carbon-hydrogen Bond for Functional Molecule Syntheses

2019 Fiscal Year Final Research Report

• Project/Area Number: 17K05855
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: Hata Takeshi 東京工業大学, 生命理工学院, 准教授 (40419271)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Keywords: 炭素－水素結合 / 遷移金属触媒 / 機能性分子 / ヘテロ環 / ヘテロπ共役分子 / パラジウム / ロジウム / ナイトレン

Outline of Final Research Achievements

This research representative developed direct conversion reactions of C-H bond by using various transition metal catalysts and applicated to efficient synthetic methods of functional materials. Specifically, the following items were carried out. (1) Facile preparation of tetrazole-containing π-conjugated compounds by using nucleophilic double addition of tetrazole derivatives and Pd-catalyzed C-H bond double activation, and their fluorescence behaviors, (2) Conjugation elongation using polycyclic benzimidazoles synthesized from nitroarenes and aryl Grignard reagents, (3) Rh-catalyzed cyclization of 1-[o-(bromoethynyl)phenyl]alkyl methyl ethers with retention of their optical activity, (4) Preparation of 2,3-dihaloindoles from a Rh catalyst and o-(2,2-dihalovinyl)aryl azides.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

1) 機能性分子に適用できるヘテロ環化合物を，ハロアセチレンやニトロ化合物などの入手容易かつ安価な原料を用いるだけでなく，合成工程数をC-H結合活性化反応により一挙に短縮化して合成できるため，コスト低減と環境負荷低減の両分野を相乗的に満たすことができる．
2) 有機合成分野の重要なトピックスの１つである不斉C-H結合活性化反応を達成し，今後の触媒的不斉反応の開発に有用な知見を与えるのみならず，持続可能社会に必要不可欠な技術として発展することができる．