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Our research focuses on synthetic organic chemistry.
Building on our original synthetic strategies, we aim to create unprecedented molecular architectures.
Discovering fascinating functions emerging from these new structures is our great motivation.
We are interested in the synthesis of a broad range of targets, from small molecules to polymers.
Below, we present selected highlights of our work.
Synthesis of 3D perfluorinated compounds using fluorine gas
Synthesis of 3D perfluorinated compounds using fluorine gas
Fully fluorinated polyhedral molecules have long been predicted to trap an electron within their framework. Despite this intriguing prediction, their synthesis had remained an unsolved challenge for many years.
We achieved the synthesis of perfluorocubane, a cubic molecule with fluorine atoms on all eight vertices, and demonstrated that it can accept an electron inside. The key to this breakthrough was the use of fluorine gas. Because fluorine gas reacts explosively with organic compounds, it has rarely been utilized in conventional organic synthesis. With an original strategy to control its reactivity, we suceeded in introducing multiple fluorine atoms into a highly strained molecular framework, leading to the synthesis of perfluorocubane.
We also synthesized cubane derivatives with six fluorine and two additional halogen atoms (X = Cl, Br, I). Remarkably, the C–X bonds in these molecules are found to be significantly shorter than those found in typical C–X single bonds.
J. Am. Chem. Soc. 2024, 146, 30686–30697.
In parallel, we are exploring compounds incorporating perfluoroadamantyl (AdF) groups. We developed dye molecules featuring AdF groups and proved that the AdF group works as a bulky electron-withdrawing substituent.
Synthesis of novel fluoropolymers
Synthesis of novel fluoropolymers
FLuoropolymers exhibit valubale properties such as water and oil repelleny and low refractive indices. However, the limited range of available fluorinated monomers and their unique reactivity often restrict structural diversity compared to non-fluorinated polymers. We address this challenge by harnessing the characteristic reactivity of oluoromonomers to create new macromolecules.
We synthesized novel fluoropolymers through the alternating copolymerization of [1.1.1]propellane and fluorinatedalkenes. These materials exhibit water- and oil- repellant property surpassing that of commercially available fluoropolymer.
ACS Macro Lett. 2024, 13, 1383–1389.
In addition, we developed a method combining the anionic ring-opening polymerization of hexafluoropropylene oxide with trifluoromethytlation, enabling simulataneous polymerization and functionalyzation.
Development of olefin metathesis using fluorinated alkenes
Development of olefin metathesis using fluorinated alkenes
オレフィンメタセシスは2つの二重結合を組み替える有用な触媒反応です。しかし，二重結合にフッ素が直接結合したフッ素化アルケンを用いると，反応は著しく進行しづらくなることが知られています。我々は，高活性触媒の開発および反応性の低さを逆手に取る反応設計により，フッ素化アルケンを用いた3種類のメタセシスを実現しました。
For the metathesis of tetrafluoroethylene (TFE), which is considered extremely unreactive, we discovered that a ruthenium catalyst bearing a seven-membered ligand (Ru7) exhibits uniquely high reactivity. This system improved the turnover number by two orders of magnitude compared to previous methods.
J. Am. Chem. Soc. 2021, 143, 20980–20987.
Building on this advance, we designed and achieved TFE-mediated ring-closing metathesis of divinyloxyalkanes, a transformation previously regarded as thermodynamically and kinetically unfavorable.
J. Am. Chem. Soc. 2024, 146, 32550–32557.
Furthermore, we exploited the low reactivity of fluoroalkenes to control sequence in polymerization. Fluorination of norbornene enabled perfectly alternating ring-opening metathesis copolymerization with dihydrofuran.
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