Innovative Synthesis of Amines from Ammonia as Nitrogen Source

2020 Fiscal Year Final Research Report

• Project/Area Number: 18K19070
• Research Category: Grant-in-Aid for Challenging Research (Exploratory)
• Allocation Type: Multi-year Fund
• Review Section: Medium-sized Section 33:Organic chemistry and related fields
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: Kuwata Shigeki 東京工業大学, 物質理工学院, 准教授 (10292781)
• Project Period (FY): 2018-06-29 – 2021-03-31
• Keywords: アンモニア / アミン / 均一系触媒 / 金属-配位子協奏機能

Outline of Final Research Achievements

In order to realize the catalytic synthesis of nitrogen-containing organic compounds from ammonia, we focused on metal-ligand bifunctional catalysts, which can cleave the N-H bond of ammonia and form C-N bonds effectively. We found that amido complexes of ruthenium and iridium react with ammonia, leading to intramolecular amination of to a C-F bond. In addition, metal complexes with different Bronsted acidity of the proton-responsive site on the ligand, such as dihydropyridylidene and trifluoromethylpyrazole ruthenium complexes, were newly synthesized to improve the activation efficiency of ammonia. Although these complexes promote the N-H bond cleavage of ammonia, the trifluoromethylpyrazole complex catalyzed isomerization of propargylic alcohols to enones.

Free Research Field

有機金属化学

Academic Significance and Societal Importance of the Research Achievements

基幹化成品として入手容易なアンモニアから、医農薬、機能性材料等の原料として幅広く利用されている含窒素化合物、とりわけ第1級アミン類を直接合成する反応は工業プロセス、精密有機合成の両面で大きな意義をもつ。本研究の成果は、その実現のための基礎的な知見を与えるともに、また、金属ー配位子協働作用に分子活性化、変換という方法論の進展につながるものである。