Development of synthetic reactions based on catalytic generation of radicals

2019 Fiscal Year Final Research Report

• Project/Area Number: 16K08188
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Hyogo University of Health Sciences
• Principal Investigator: Miyabe Hideto 兵庫医療大学, 薬学部, 教授 (10289035)
• Co-Investigator(Kenkyū-buntansha): 甲谷 繁 兵庫医療大学, 薬学部, 教授 (00242529)
• Project Period (FY): 2016-04-01 – 2020-03-31
• Keywords: 有機合成 / 触媒 / 光触媒 / 有機触媒 / ラジカル / 酸化 / 還元

Outline of Final Research Achievements

The catalytic radical reactions were developed by the use of photocatalysts having the potential to induce the oxidation or reduction. (1) The catalytic and chemoselective oxidation of cinnamaldehyde derivatives was achieved by using rhodamine 6G as an organophotocatalyst. The catalysis using rhodamine 6G promoted the oxidation of olefin moiety in a chemoselective manner. In contrast, the cooperation between rhodamine 6G and N-heterocyclic carbene (NHC) allowed the oxidative esterification of formyl group. (2) The chiral TiO2 catalysts were developed for the asymmetric reduction of aromatic ketones. When a chiral mandelic acid-adsorbed TiO2 catalyst was used, the alcohols were obtained with a reasonable enantioselectivities. (3) When charge-transfer complex between iodine and amines was employed, the radical addition reactions proceeded under visible light irradiation in the absence of the typical photocatalysts.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

これからの有機合成は、環境に調和適合した合成に進化する必要がある。現在のラジカル合成化学では、ラジカル種の発生に、過剰の試薬を用いる場合が多く、環境への負荷が大きい。ラジカル合成化学を飛躍的に発展させるためには、ラジカル反応の触媒化が不可欠である。本研究は、光触媒を活用した新しい方法に基づき、ラジカル反応の触媒化を研究し、有機化学分野や触媒化学分野の発展に貢献する。