Development of N-H insertion reactions between carbenoids and ammonia and its application toward direct amino acid synthesis

2023 Fiscal Year Final Research Report

• Project/Area Number: 21K14634
• Research Category: Grant-in-Aid for Early-Career Scientists
• Allocation Type: Multi-year Fund
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Nihon University
• Principal Investigator: SAITO Hiroaki 日本大学, 薬学部, 講師 (30385976)
• Project Period (FY): 2021-04-01 – 2024-03-31
• Keywords: 触媒化学 / 遷移金属の可溶化 / アンモニア等価体 / ポリオール型錯体 / カルベン挿入反応 / 炭素ー窒素結合の構築

Outline of Final Research Achievements

The purpose of this study is to develop a methodology that allows ammonia molecules to be introduced directly into carbenes. Throughout the research period, we verified the modification of complex functions aimed at high efficiency, the synthesis of water-soluble complexes, and the direct synthesis of amino acids by using ammonia and its equivalents. It was found that when the ammonia molecule itself is used as a nitrogen source, the target product can be obtained with a yield of about 20%. In addition, when verification was carried out using an ammonia equivalent, it became possible to improve the efficiency of the reaction by using imines. In addition, we prepared a water-soluble rhodium(II) complex with the intention of using ammonia water for the reaction, and succeeded in preparing a complex with a polyol structure and high solubility in water.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

環境保護の観点から、化学合成における工程数の削減は意義がある。本研究では医薬品分子によくみられる窒素原子の導入法に関する研究を行ったものである。この反応には反応条件の検証と共に、触媒の設計と合成も重要なものとなる。本研究を通じて調製した水溶化ロジウム錯体は、カルベン反応でまず性能を検証することとなるが、一方で類似の三次元構造をもつ二核錯体はカップリング反応において有用な例が報告されつつあり、今後、同様の反応に応用できる可能性を秘めたものである。