| Project/Area Number |
18K05101
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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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| Review Section |
Basic Section 33020:Synthetic organic chemistry-related
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| Research Institution | University of Toyama |
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Principal Investigator |
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| Co-Investigator(Kenkyū-buntansha) |
是永 敏伸 岩手大学, 理工学部, 教授 (70335579)
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| Project Period (FY) |
2018-04-01 – 2021-03-31
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| Project Status |
Completed (Fiscal Year 2020)
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| Budget Amount *help |
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2020: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2018: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
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| Keywords | パラジウム / ケイ素 / アリル化反応 / アリルパラジウム / ホモアリルアルコール / 転位 / アリルシラン / 1,2-転位 |
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| Outline of Final Research Achievements |
The palladium-catalyzed reaction of γ-silylated allyl acetates with water in the presence of CsF induced a previously unprecedented 1,2-shift of a substituent on silicon to produce allylsilanes in situ. The catalytic activity of the palladium increased when using an electron-poor phosphine ligand possessing fluorinated substituents. Further investigation of the reaction revealed that the approximate order of the migratory aptitude of groups from silicon was PhC≡C, allyl > Bn > Ph, vinyl > alkyl (Me, Et). A density functional theory study was employed to explore the reaction mechanism. Finally, Hosomi-Sakurai-type allylation of aldehydes with in situ-generated α,γ-disubstituted allylsilanes was also investigated. While intramolecular Hosomi-Sakurai-type allylation afforded homoallylic alcohols as mixtures of regioisomers and diastereomers, intramolecular version proceeded regioselectively and provided the corresponding homoallylic alcohols with good to high diastereoselectivity.
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| Academic Significance and Societal Importance of the Research Achievements |
ケイ素官能基を持つアリルパラジウムにおいて，有機ケイ素化合物とアリルパラジウム錯体の特性を協同的に利用することで，シリル基上の有機基の1,2-転位が起こる興味深い知見を得た。また，アリルシランによるアルデヒドのアリル化反応をワンポットで行う新規分子変換反応も確立することができた。本研究によって得られた成果は，アリルケイ素およびアリルパラジウムの有用性を格段に向上させることに貢献する。このように，反応中間体に立脚した研究より得られる新しい発見および新規触媒的分子変換反応への展開は，有機合成化学に新たな知見を提供するものであり，関連する学術分野の発展に大きく貢献することが期待される。
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