2014 Fiscal Year Final Research Report
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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| 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 |
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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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| Free Research Field |
有機合成化学
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