2019 Fiscal Year Final Research Report
Copper-catalyzed metalation reactions based on precise control of metal-Lewis acidity
| Project/Area Number |
17K05864
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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 |
Synthetic chemistry
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| Research Institution | Hiroshima University |
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Principal Investigator |
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| Project Period (FY) |
2017-04-01 – 2020-03-31
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| Keywords | ルイス酸性制御 / ボリル化 / スタニル化 / 銅触媒 / クロスカップリング |
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| Outline of Final Research Achievements |
Copper-catalyzed borylative substitution reaction of allylic phosphates with diaminonaphtalene-substituted unsymmetrical diboron has been developed. A diaminonaphthalene-substituted boron moiety with diminished Lewis acidity has been found to be installed chemoselectively into the gamma position of the allylic phosphates, leading to the formation of various allylic boron compounds in high yields. In addition, we have succeeded in synthesizing an anthranilamide-substituted unsymmetrical diboron, which can be utilized for palladium-catalyzed borylative substitution of aryl halides. The resulting anthranilamide-sustituted aryl boron compounds have turned out to undergo direct Suzuki-Miyaura coupling without prior acidic deprotection. We have also achieved copper-catalyzed arylstannylation of arynes, which provides direct access to diverse biarylstannanes.
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| Free Research Field |
有機合成化学，有機金属化学
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| Academic Significance and Societal Importance of the Research Achievements |
元来ルイス酸であるホウ素のルイス酸性を適切な置換様式で抑制し，それに付随するユニークな化学選択性を活かした触媒的ホウ素化反応群の開発に成功した．こうして直截的に得られるルイス酸性抑制型有機ホウ素化合物は，従来の有機ホウ素化合物に比べて空気や水に対し格段に安定となり，取り扱い・実用性の面で優位となる．一方でルイス酸性抑制は，有機ホウ素化合物のホウ素を起点とした変換の反応性を下げるためこれまで脱保護を要していたが，本研究ではルイス酸性抑制ホウ素をそのままクロスカップリングに利用する手法も確立した．今後の有用分子合成に広く利用可能な合成手法であるといえる．
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