Synthesis of Hypervalent Organobromine and Chlorine Compounds by Electrochemical Approaches and Their Use in Organic Synthesis

2022 Fiscal Year Final Research Report

• Project/Area Number: 20H02720
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
• Research Institution: The University of Tokyo
• Principal Investigator: Miyamoto Kazunori 東京大学, 大学院薬学系研究科(薬学部), 准教授 (40403696)
• Project Period (FY): 2020-04-01 – 2023-03-31
• Keywords: 超原子価 / 塩素 / 臭素 / 安定化 / 酸化

Outline of Final Research Achievements

In contrast to hypervalent organoiodine compounds, widely used in modern organic synthesis, hypervalent organobromine and chlorine analogs remain to be explored, probably due to the lack of practical synthetic methods. In this study, we have extensively investigated molecular designs, solvent systems, and oxidation methods in order to establish new synthetic methods for hypervalent bromine and chlorine compounds. In particular, several important findings were found during the process of the study on the oxidation methods involving anodic oxidation. For example, it was found that hypervalent organobromane(III) can be efficiently synthesized by using potent oxidant such as xenon difluoride under optimized conditions, which has been considered difficult to use for the oxidation of organobromine(I) compounds.

Free Research Field

有機化学、典型元素化学、有機合成化学

Academic Significance and Societal Importance of the Research Achievements

本研究で得られた成果は、いまだ不明な点の多い超原子価臭素・塩素の化学を切り拓くための重要な発見を含んでいる。具体的には、入手が難しく危険を伴う三フッ化臭素などの前駆体の使用が必須であった超原子価臭素・塩素化合物の合成を容易に実現できるようになり、また、環状構造の導入により安定性を付与することで、多種多様な誘導体化が可能になった。これにより同族のヨウ素類縁体との直接の性質の比較が可能になり、周期律表の同族元素間のうち、最後まで明らかにされていなかったハロゲン族元素の超原子価化合物に眠っている特徴や法則を解明できることが最大の成果である。