Study on the control of reactivity of thiazolinylidene NHCs by effective shielding by bicyclo-skeleton

2021 Fiscal Year Final Research Report

• Project/Area Number: 19K06998
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 47010:Pharmaceutical chemistry and drug development sciences-related
• Research Institution: Kumamoto University
• Principal Investigator: Ishizuka Tadao 熊本大学, 大学院生命科学研究部(薬), 教授 (60176203)
• Project Period (FY): 2019-04-01 – 2022-03-31
• Keywords: カルベン / チアゾリウム

Outline of Final Research Achievements

The NS-type NHC precursor, thiazolium salt with bicyclo[2.2.2] octane skeleton, was successfully synthesized after various reaction condition trials, but the carbene generation by the base did not lead to the isolation of a stable compound as in the NN system.However, it was suggested that carbenes were generated, and we were able to attempt the formation of silver complexes and reactions with copper complexes generated in the system. Although we have not reached the point of obtaining reproducible results, we believe that we have established a foundation for further detailed studies.
We have also succeeded in introducing naphthalene and anthracene ring-systems into the bicyclo[2.2.1] heptane skeleton, although in the NN system, and were able to compare their electronic properties as ligands by X-ray structural analysis and IR-spectrum measurement of the Ir-complex. We have reached the preliminary stage of the conversion to the NS system.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

カルベン種としても報告例の少ないNS系NHCである上にビシクロ環系であることから、得られる情報はすべて学術的に重要である。NN系において従来のNHCとは異なる結果がえられているために、ビシクロ環がもたらす影響を調べる上で骨格が同様のNS系の挙動を調査することは意義深い。新規条件での反応が可能となれば、合成化学の進歩につながり社会的な意義もあると考えられる。