Hydroamination of alkenes with dinitrogen and titanium polyhydrides

• 成果类型: Article
• 署名作者: Shima, Takanori; Zhuo, Qingde; Zhou, Xiaoxi; Wu, Ping; Owada, Ryota; Luo, Gen; Hou, Zhaomin
• 署名单位: RIKEN; RIKEN; Anhui University
• 刊物名称: Nature
• ISSN/ISSBN: 0028-4827
• DOI: 10.1038/s41586-024-07694-5
• 发表日期: 2024-08-08
• 关键词: bond formation; carbon-dioxide; side-on; cleavage; nitrogen; conversion; n-2; functionalization; activation; Fixation

摘要

An ideal synthesis of alkyl amines would involve the direct use of abundant and easily accessible molecules such as dinitrogen (N2) and feedstock alkenes1-4. However, this ambition remains a great challenge as it is usually difficult to simultaneously activate both N2 and a simple alkene and combine them together through carbon-nitrogen (C-N) bond formation. Currently, the synthesis of alkyl amines relies on the use of ammonia produced through the Haber-Bosch process and prefunctionalized electrophilic carbon sources. Here we report the hydroamination of simple alkenes with N2 in a trititanium hydride framework, which activates both alkenes and N2, leading to selective C-N bond formation and providing the corresponding alkyl amines on further hydrogenation and protonation. Computational studies reveal key mechanistic details of N2 activation and selective C-N bond formation. This work demonstrates a strategy for the transformation of N2 and simple hydrocarbons into nitrogen-containing organic compounds mediated by a multinuclear hydride framework. A trititanium hydride framework is used to achieve direct hydroamination of simple feedstock hydrocarbons with inert nitrogen gas to obtain the corresponding alkyl amines.