Synthesis of chiral helical polymers by highly selective photocyclic aromatization(SCAT) using light as asymmetric source, and asymmetric amplification
| Project/Area Number |
16K05790
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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 |
Polymer chemistry
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| Research Institution | Niigata University |
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Principal Investigator |
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| Co-Investigator(Kenkyū-buntansha) |
青木 俊樹 新潟大学, 自然科学系, 教授 (80212372)
金子 隆司 新潟大学, 自然科学系, 教授 (90272856)
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| Project Period (FY) |
2016-04-01 – 2019-03-31
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| Project Status |
Completed (Fiscal Year 2018)
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| Budget Amount *help |
¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2018: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2017: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2016: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
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| Keywords | 光学活性高分子 / らせん高分子 / らせん巻き方向選択的分解反応 / らせん選択重合 / 円偏光 / 光環化芳香族化反応 / 片巻きらせん高分子 / 環化芳香族化分解 / らせん巻方向選択的分解 / 速度論的光学分割 / 絶対不斉合成 / キラル増幅 / キラル転写 / キラル / 光環化反応 / 不斉増幅 |
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| Outline of Final Research Achievements |
In this project, at first synthesis of an optically active one-handed helical polymer from a racemic helical polymer using only circularly polarized light(CPL) as an asymmetric source without using an optically active chemical substance was achieved, and then by using the obtained a one-handed helical polymer as chiral cocatalyst which was generated by CPL as an asymmetric source , we achieved helix-sense-selective polymerization(HSSP) of achiral phenylacetylene derivatives. It has been revealed that a racemic helical polymer obtained from a phenylacetylene monomer having a planar substituent such as a diphenylazomethine group is efficiently decomposed in helix-sense-selective manner by CPL irradiation to give a chiral one-handed helical polymer. In addition, using a one-handed helical polymer obtained by HSSP as a chiral cocatalyst (asymmetric source), a new one-handed helical polymer was successfully obtained by HSSP (chiral transfer).
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| Academic Significance and Societal Importance of the Research Achievements |
人工的にキラル分子を合成する際には、キラルの源となるものがなければ、右手、左手に相当する両方のエナンチオマー(鏡像異性体)が生成する。一方、自然界に存在するアミノ酸や糖などの生体分子は一方のエナンチオマーのみからなるホモキラリティーな状態にあるが、どのようにしてホモキラリティーが生まれたかやキラルの源は何であったかについては謎であり、生命誕生の起因と並んで非常に興味がもたれている。本研究は自然界のホモキラリティーの起源やホモキラリティーに至る過程のモデルとして学術的意義があるだけでなく、光不斉反応による光学活性高分子の入手法を新たに提供でき、さらに光学分割膜といった実用への利用も容易である。
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Report
(4 results)
Research Products
(35 results)
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[Journal Article] [Rh(L-alanine)(1,5-Cyclooctadiene)] Catalyzed Helix-Sense-SelectivePolymerizations of Achiral Phenylacetylenes2018
Author(s)
Qingyu Wang, Hongge Jia, Yongqiang Shi, Liqun Ma, Guoxing Yang, Yazhen Wang, Shuangping Xu, Jianjun Wang, Yu Zang, Toshiki Aoki,
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Journal Title
Polymers
Volume: 10(11)
Issue: 11
Pages: 1223-1223
DOI
Related Report
Peer Reviewed / Open Access / Int'l Joint Research
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