Mechanistic study on anti-Wacker-type cyclization and application to synthesis of biologically active polycyclic compounds
| Project/Area Number |
24590004
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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) |
2012-04-01 – 2015-03-31
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| Project Status |
Completed (Fiscal Year 2014)
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| Budget Amount *help |
¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000)
Fiscal Year 2014: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Fiscal Year 2013: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2012: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
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| Keywords | アンチWacker型環化反応 / 環化機構 / パラジウム / 有機ボロン酸 / トランスメタル化 / ハオウアミン / haouamine / ホスフィン配位子 / 位置選択性 / 置換基効果 / 環化メカニズム / haouamine B |
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| Outline of Final Research Achievements |
We have developed palladium(0)/monophosphine-catalyzed trans-selective arylative cyclization reactions of alkyne-aldehydes with organoboron reagents leading to 3-substituted 2-cyclohexen-1-ols and/or 2-alkylidene-cyclopentan-1-ols. The remarkable trans selectivity of the processes would result from the novel reaction mechanism involving ‘anti-Wacker-type’-oxidative addition followed by transmetalation. The proposed mechanism is supported by an experimental result that (E)-8-phenyloct-7-en-5-ynal undergoes a reductive cyclization in the absence of organometallic agents. Formal synthesis of haouamine A and B was effectively achieved by 1) large-scale synthesis of indeno-tetrahydropyridines through the ‘anti-Wacker’-type cyclization and intramolecular ‘Friedel-Crafts’-type reaction, 2) Suzuki-Miyaura cross-coupling with 2-boryl-2-cyclohexen-1-one ethylene acetal, and 3) (cyanomethyl)trimethylphosphonium iodide-mediated macrocyclization of amino alcohol intermediates.
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Report
(4 results)
Research Products
(31 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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[Journal Article] Reconstitution of Peptidoglycan Cross-Linking Leads to Improved Fluorescent Probes of Cell Wall Synthesis2014
Author(s)
Lebar, Matthew D.; May, Janine M.; Meeske, Alexander J.; Leiman, Sara A.; Lupoli, Tania J.; Tsukamoto, Hirokazu; Losick, Richard; Rudner, David Z.; Walker, Suzanne; Kahne, Daniel
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Journal Title
Journal of the American Chemical Society
Volume: 136
Issue: 31
Pages: 10874-10877
DOI
Related Report
Peer Reviewed
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