Controlled organic synthesis utilizing propylene polymerization catalysts

2018 Fiscal Year Final Research Report

• Project/Area Number: 15H03807
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: The University of Tokyo
• Principal Investigator: Nozaki kyoko 東京大学, 大学院工学系研究科(工学部), 教授 (60222197)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Keywords: 有機化学 / プロピレン / オリゴマー化

Outline of Final Research Achievements

By using metallocene catalysts, oligomers of propylene were obtained starting from dialkyl zinc as an initiator with extremely high stereospecificity. More importantly, after oxidation of the oligomerization products, the mixture of alcohols with different chain-lengths were successfully purified by reverse-phase high-performance liquid chromatography.
Both all syn- and all anti- structures were obtained employing C2-symmetric and Cs-symmetric catalysts, respectively, as was reported for the propylene polymerization. In case for the C2-symmetric complex, optical resolution of the chiral complex allowed the asymmetric synthesis and thus a single enantiomer was obtained in over 99% ee.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

単離したall-synオリゴマーは灰色ガンの油脂の主要成分である（2R、4R、6R、8R）-2,4,6,8-テトラメチルデカン酸合成に、all-antiオリゴマーは昆虫Antitrogus parvulusラのホルモンの合成中間体である、rel-(2R,4S,6R,8S)-2,4,6,8‐テトラメチルウンデカン‐1‐オール合成に用いることができた。これらの化合物の生合成経路がプロピオニルＣｏＡによって媒介されるクライゼン縮合であることを考慮すると、本合成はビルディングブロックとして同じＣ ３単位を使用しており、同時に得られる他のオリゴマーは生物学的活性を発現し得る。