Mechanistic study on anti-Wacker-type cyclization and application to synthesis of biologically active polycyclic compounds
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- TSUKAMOTO Hirokazu
- Principal Investigator
- 東北大学
About this project
- Japan Grant Number
- JP24590004
- Funding Program
- Grants-in-Aid for Scientific Research
- Funding organization
- Japan Society for the Promotion of Science
- Project/Area Number
- 24590004
- Research Category
- Grant-in-Aid for Scientific Research (C)
- Allocation Type
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- Multi-year Fund
- Review Section / Research Field
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- Biological Sciences > Medicine, Dentistry, and Pharmacy > Pharmacy > Chemical pharmacy
- Research Institution
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- Tohoku University
- Project Period (FY)
- 2012-04-01 〜 2015-03-31
- Project Status
- Completed
- Budget Amount*help
- 5,200,000 Yen (Direct Cost: 4,000,000 Yen Indirect Cost: 1,200,000 Yen)
Research Abstract
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.
Keywords
Details 詳細情報について
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- CRID
- 1040000782211514240
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- Text Lang
- ja
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- Data Source
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- KAKEN
