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Synthesis of visible-light-active hypervalent iodines

Research Project

Project/Area Number 18K14863
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 47010:Pharmaceutical chemistry and drug development sciences-related
Research InstitutionChiba University

Principal Investigator

Nakajima Masaya  千葉大学, 大学院薬学研究院, 助教 (70802677)

Project Period (FY) 2018-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2019: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2018: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords光化学 / 超原子価ヨウ素 / 重原子 / 可視光 / 可視光励起
Outline of Final Research Achievements

We performed a computational design and actual synthesis of visible-light-active hypervalent iodine. The synthesized PADI proceeded with the oxidation reaction under visible light irradiation. Moreover, it was proved by experiments, spectroscopic measurements, and quantum calculations that the photoexcitation mechanism of PADI was a “direct S0 → Tn transition” that was thought not to proceed. We also demonstrated that this mechanism can be extended to hypervalent iodine compounds in general and suggested that it can be extended to monovalent iodine and bromine-containing molecules. This finding has opened up new possibilities for studying photoreactions of molecules containing heavy atoms.

Academic Significance and Societal Importance of the Research Achievements

一般に光反応は「S0→Sn遷移」という機構のみが考慮されてきており、多くの光反応の教科書には「S0→Tn遷移は進行しない」と明記されている。私は、本研究課題において合成した超原子価ヨウ素化合物が、その「S0→Tn遷移」によって光反応を起こしていることに気づいた。そしてこの偶然の発見は、その分子のみに起こるものではなく、ヨウ素以外にも重い原子を有している分子においても共通に現れる現象であり、これまで「S0→Tn遷移は進行しない」とされてきた光反応の常識を覆すことに成功した。これにより、これまで紫外線が必須であると考えられていた反応も、より低エネルギーで安全な可視光を用いることができるようになる。

Report

(3 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report

Research Products

(3 results)

All 2020 2019

All Journal Article (3 results) (of which Peer Reviewed: 3 results)

  • [Journal Article] A Direct S 0 →T n Transition in the Photoreaction of Heavy‐Atom‐Containing Molecules2020

    • Author(s)
      Nakajima Masaya、Nagasawa Sho、Matsumoto Koki、Kuribara Takahito、Muranaka Atsuya、Uchiyama Masanobu、Nemoto Tetsuhiro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: - Pages: 6847-6852

    • DOI

      10.1002/anie.201915181

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Visible-Light-Induced Metal-/Photocatalyst-Free C?H Bond Imidation of Arenes2020

    • Author(s)
      Kuribara Takahito、Nakajima Masaya、Nemoto Tetsuhiro
    • Journal Title

      Organic Letters

      Volume: 22 Pages: 2235-2239

    • DOI

      10.1021/acs.orglett.0c00433

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Determination of the best functional and basis sets for optimization of the structure of hypervalent iodines and calculation of their first and second bond dissociation enthalpies2019

    • Author(s)
      Matsumoto Koki、Nakajima Masaya、Nemoto Tetsuhiro
    • Journal Title

      Journal of Physical Organic Chemistry

      Volume: 32

    • DOI

      10.1002/poc.3961

    • Related Report
      2019 Annual Research Report 2018 Research-status Report
    • Peer Reviewed

URL: 

Published: 2018-04-23   Modified: 2021-02-19  

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