Development of site-selective catalytic reactions controlled by ligands and their application to syntheses of multisubstituted compounds
| Project/Area Number |
17K08214
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | University of Shizuoka |
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Principal Investigator |
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| Project Period (FY) |
2017-04-01 – 2020-03-31
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| Project Status |
Completed (Fiscal Year 2019)
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| Budget Amount *help |
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2017: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
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| Keywords | 位置選択的 / 配位子 / パラジウム / インドール / ピロール / アリール化 / 脱芳香族化 / 位置選択性 / 有機化学 / 触媒 / クロスカップリング |
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| Outline of Final Research Achievements |
In this study, ligand-controlled C3-selective arylation of N-nonsubstituted indoles was achieved using a catalyst derived from palladium and dihydroxyterphenylphosphine (DHTP). In case of 3-substituted indole, dearomative C3-arylation proceeded to afford indolenines, which can be converted into indolines. In addition, 2,3-disubstituted benzofurans were synthesized from readily available 2-chlorophenols by using Pd-DHTP catalyst. Based on these reactions, ligand-controlled site-selective arylation of N-nonsubstituted 1H-pyrrole was developed. By changing the ligand, C2- and C3-selectivity was efficiently switched. From 2,5-disubstituted 1H-pyrroles, dearomative C2-arylation proceeded and 2,2,5-trisubstituted 2H-pyrroles were successfully obtained. Use of these site-selective arylation enabled efficient synthesis of various multisubstituted indoles and pyrroles. These methods will be powerful tools for rapid and efficient synthesis of multisubstituted compounds.
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| Academic Significance and Societal Importance of the Research Achievements |
本研究を通じて、従来の方法のように基質の性質を利用して位置選択性を制御するのではなく、金属触媒とともに用いる配位子により位置選択性を制御することで、基質適用範囲の拡大が期待できる。また、適切な構造の配位子を既存の配位子から選択したり、新規配位子をデザインすることで、様々な反応への展開が容易になると考えられる。有機合成化学において重要な合成ターゲットである種々の多置換複素環化合物のワンポット合成法が確立すれば、化合物ライブラリー合成や医薬品の生産において強力な手法となると考えられる。また、合成の効率化により試薬やエネルギーの使用量が減少し、環境への負荷の低減につながると期待される。
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Report
(4 results)
Research Products
(19 results)
