| 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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| 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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