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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| Project Status |
Completed (Fiscal Year 2017)
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| Budget Amount *help |
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
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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 / エナンチオ選択的アンチWacker型環化反応 / アルキン－カルボニル / 有機亜鉛試薬 / キラルルイス酸 / アルキン－エナール / アリールボロン酸 / パラジウム－ジフェニルプロリノール共触媒 / ジインの非対称化 / アレニルホスフェートの動的速度論的分割反応 / キラルブレンステッド酸 |
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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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Report
(4 results)
Research Products
(36 results)
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[Journal Article] Total Synthesis and Structure Determination of JBIR-108 - A 2-Hydroxy-2-(1-hydroxyethyl)-2,3-dihydro-3(2H)-furanone Isolated from Streptomyces gramineus IR087Pi-42015
Author(s)
Fujiwara, Koichi; Tsukamoto, Hirokazu; Izumikawa, Miho; Hosoya, Takahiro; Kagaya, Noritaka; Takagi, Motoki; Yamamura, Hideki; Hayakawa, Masayuki; Shin-ya, Kazuo; Doi, Takayuki
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Journal Title
Journal of Organic Chemistry
Volume: 80
Issue: 1
Pages: 114-132
DOI
Related Report
Peer Reviewed
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