日本理化学研究所Hou, Zhaomin团队报道了烯烃与二氮和钛多氢化物的氢胺化反应。相关研究成果发表在2024年6月17日出版的《自然》。

烷基胺的理想合成涉及直接使用丰富且易于获得的分子，例如二氮（N₂）和原料烯烃。然而，这一雄心仍然是一个巨大的挑战，因为通常很难同时激活N₂和简单的烯烃，并通过C-N键形成将它们结合在一起。目前，烷基胺的合成依赖于使用通过Haber Bosch工艺生产的氨和预功能化亲电碳源。

该文中，研究人员报道了简单烯烃在氢化氚骨架中与N₂的加氢胺化，这激活了烯烃和N₂，导致选择性形成C-N键，并在进一步氢化和质子化时提供相应的烷基胺。计算研究揭示了N₂活化和选择性C-N键形成的关键机制细节。

该项工作展示了一种通过多核氢化物框架，将N₂和简单烃转化为含氮有机化合物的策略。

附：英文原文

Title: Hydroamination of alkenes with dinitrogen and titanium polyhydrides

Author: Shima, Takanori, Zhuo, Qingde, Zhou, Xiaoxi, Wu, Ping, Owada, Ryota, Luo, Gen, Hou, Zhaomin

Issue&Volume: 2024-06-17

Abstract: 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 C?N bond formation. Currently, the synthesis of alkyl amines relies on the use of ammonia produced via the Haber-Bosch process and prefunctionalised 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.

DOI: 10.1038/s41586-024-07694-5

Source: https://www.nature.com/articles/s41586-024-07694-5