Structure Control of Open-chain Oligopyrroles Leading to Chirality-related Functions
| Project/Area Number |
24550050
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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 |
Organic chemistry
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| Research Institution | Kobe University |
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Principal Investigator |
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| Project Period (FY) |
2012-04-01 – 2016-03-31
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| Project Status |
Completed (Fiscal Year 2015)
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| Budget Amount *help |
¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000)
Fiscal Year 2014: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2013: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2012: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
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| Keywords | らせん不斉 / オリゴピロール / ヘリケート / パラジウム錯体 / 複核錯体 / らせん構造 / ピロール / キラリティー / ヘリシティー / ポルフィリノイド / へリシティー / 不斉転写 / 酸化還元 |
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| Outline of Final Research Achievements |
This work aimed at creating new oligopyrrole helicates with high helical sense bias leading to chirality-related functions. The hexapyrrole-α,ω-dialdehyde was synthesized and easily converted into the dipalladium helicates of hexapyrrole-α,ω-diimines by using optically active amines. These helicates can take a couple of conformations, but the α,ω-diimine derived from (R)-1-cyclohexylethylamine induced P-helical closed C2 form in 85% diastereoselectivity. An appropriate choice of the substitution pattern in the 2,2’-bipyrrole unit resulted in full bias of P-helical sense. Introduction of 1,3- and 1,4-phenylene spacer into the 2,2’-bipyrrole unit also caused more than 95% diastereoselectivity of the one-handed helicate by using a variety of optically active amines. The one-handed hexapyrrole helicate underwent reversible one-electron redox at less positive potentials accompanied by the drastic changes of the strong CD signals at 600 - 800 nm.
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Report
(5 results)
Research Products
(32 results)
