2022 Fiscal Year Final Research Report
Stereoselective Synthesis of Chiral Substituted-Cyclobutanes and Ladderanes
| Project/Area Number |
20H03360
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Review Section |
Basic Section 47010:Pharmaceutical chemistry and drug development sciences-related
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| Research Institution | Hokkaido University |
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Principal Investigator |
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| Project Period (FY) |
2020-04-01 – 2023-03-31
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| Keywords | シクロブタン / ラダラン / ロジウム / ルテニウム / コバルト / メタラサイクル |
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| Outline of Final Research Achievements |
In this project, we aimed to develop stereoselective synthesis of polysubstituted cyclobutane derivatives and radarane derivatives. As a result, we succeeded in synthesizing spiro-cyclobutane derivatives via Rh-catalyzed enantioselective cyclization of enynes via Csp3-H bond activation triggered by formation of rhodacycle intermediates. Also, we succeeded in synthersis of sulfur-containing radarane derivatives and boron-containing multisubstituted cyclobutane derivatives through Ru-catalyzed cyclization of allenynes. Furthermore, to avoid the use of the rare metal such as Rh, we started a basic research on Co-catalyzed reaction via cobaltacycle, resulting in develping Co-catalyzed reductive cyclization of enynes using hydrogen (H2) as a reducing agent.
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| Free Research Field |
有機合成化学
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| Academic Significance and Societal Importance of the Research Achievements |
シクロブタン骨格は天然物などにも含まれ，創薬においてもオレフィンやベンゼンの生物学的等価体としての利用も期待される骨格である．またシクロブタン環が連結し「はしご状」となったラダラン骨格をもつ天然物も最近発見され，その機能にも興味が持たれている．一方，多置換シクロブタンの立体選択的合成法や光学活性体での合成法は限られており，さらにラダラン骨格に関しては合成例が極めて少ない．本研究では，例のないスピロ骨格を持つシクロブタン誘導体の不斉合成や，官能基化の手掛かりとなる硫黄やホウ素を骨格内に含むラダラン誘導体の合成に成功しており，その学術的意義や社会的意義は大きい．
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