A new strategy for the synthesis of heavier multiply bonded compounds utilizing the cavity of calix[4]arene

2021 Fiscal Year Final Research Report

• Project/Area Number: 20K15265
• Research Category: Grant-in-Aid for Early-Career Scientists
• Allocation Type: Multi-year Fund
• Review Section: Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
• Research Institution: Ochanomizu University (2021); Chuo University (2020)
• Principal Investigator: KUWABARA Takuya お茶の水女子大学, 基幹研究院, 講師 (60768654)
• Project Period (FY): 2020-04-01 – 2022-03-31
• Keywords: カリックスアレーン / ゲルミレン / スタンニレン / プルンビレン

Outline of Final Research Achievements

This research aims to establish a new strategy for the synthesis of heavier multiply bonded compounds utilizing the cavity of calix[4]arene. We have successfully synthesized calix- and thiacalix[4]arene-tetrylene complexes, which would be good precursors for the target heavier vinylidenes. It is of note that the thiacalixarene-stannylenes and -plumbylenes are isolated as only exo-isomer, in which the metal center is situated outside the cavity. This is in contrast to the fact that the calix[4]arene counterparts have been isolated as not only exo-isomers but endo-isomers, where the metal center is inside the cavity.
Unfortunately, these tetrylenes are inert toward various substrates such as SnCl2, PbCl2, N2O, and pyridine N-oxide, and hence, the synthesis of target compounds have not been achieved so far. However, through this research, we have contributed the development of the chemistry of diaryloxytetrylene embedded in calix[4]arene, thiacalix[4]arene, and methylenedophenols.

Free Research Field

元素化学

Academic Significance and Societal Importance of the Research Achievements

本研究で扱ったスタンニレンおよびプルンビレンはいずれも反応性が乏しく、目的物の合成には至らなかった。しかし、その原因が２つの酸素置換基による二価化学種の安定化によるものであることがわかったため、この知見を今後の重いビニリデン合成の分子設計指針に活用することで、重いビニリデンだけでなく含高周期14族元素未踏分子の合成へと繋がると期待される。