2017 Fiscal Year Final Research Report
Development of enantioselective 'anti-Wacker'-type cyclizations
| Project/Area Number |
15K07849
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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 | Tohoku University |
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Principal Investigator |
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| Project Period (FY) |
2015-04-01 – 2018-03-31
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| Keywords | 不斉合成 / アルキン / アレン / 共役エンイン / アレニルアルコール |
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| Outline of Final Research Achievements |
We attempted the following palladium(0)-catalyzed 'anti-Wacker'-type cyclizations of alkyne- or allene-containing electrophiles with organometallics: 1) asymmetric synthesis of cycloalkenols using chiral Lewis acid cocatalyst, 2) desymmetrization of diyne-aldehydes using chiral monophosphine ligand, and 3) chirality transfer of axially chiral allenic amines in situ generated by dynamic kinetic asymmetric allylic alkylation of primary amines with allenyl phosphates.
We also developed asymmetric alkylative cyclizations of alkyne-enals with organoboronic acids under the catalysis consisting of palladium, diarylprolinol, and catechol. Furthermore, we also demonstrated that pronucleophiles such as dimethyl malonate underwent not only 1,4-addition to conjugate enynes but also nucleophilic substitution with allenic alcohols under palladium catalysis in methanol solvent. The use of ketones as the pronuleophile in the latter reaction resulted in the direct formation of dihydrofurans.
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| Free Research Field |
有機合成化学
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