2026-11-10 九州大学
図1. 本研究のコンセプト
保護基を触媒として活用する新たな合成戦略
＜関連情報＞
- https://www.kyushu-u.ac.jp/ja/researches/view/1620
- https://pubs.acs.org/jacsat/article-abstract/148/43/47545/5455915/Protecting-Groups-as-Catalysts-Direct-Synthesis-of
保護基を触媒として用いる：カルボニル触媒によるアンモニアからの第一級アミンの直接合成 Protecting Groups as Catalysts: Direct Synthesis of Primary Amines from Ammonia under Carbonyl Catalysis
Kazuki Shimozono; Nao Nishimoto; Takuma Tagami; Takashi Ohshima
Journal of the American Chemical Society Published:October 22, 2026
DOI:https://doi.org/10.1021/jacs.6c18373
Abstract
Primary amines are indispensable building blocks in pharmaceuticals, agrochemicals, and functional materials, yet their direct, modular synthesis from ammonia remains challenging. Here we report a carbonyl catalysis strategy that enables the direct synthesis of structurally complex primary amines from ammonia by integrating the conventional multistep sequence of protection, N–H functionalization, and deprotection into a single catalytic cycle. As a proof of concept, amino-trifluoromethylation of alkenes using ammonium salts and Togni reagent afforded a wide range of β-trifluoromethylated primary amines, including derivatives of complex natural products. 1,8-Diazafluorenone was uniquely competent as a carbonyl catalyst, highlighting the critical role of catalyst design in ammonia transformation. Mechanistic studies suggest that its distinctive electronic structure facilitates the formation of the N–H ketimine intermediate, a prerequisite for catalytic turnover. These findings establish carbonyl catalysis as a platform for the direct transformation of ammonia and demonstrate how protecting groups can function as catalysts.
