韩国科学技术院Sukbok Chang报道了融合NiH催化和内球金属-类硝基烯转移的炔烃氢酰胺化反应。 相关研究成果发表在2021年4月9日出版的《美国化学会杂志》。

利用金属氢化物的正式加氢胺化/加氢酰胺化是从不饱和烃中制备有价值的含氮化合物的一种有吸引力的合成工具。尽管在这一领域烯烃的功能化取得了重大进展，但由于关键的金属烯基中间体选择其他反应途径的高度可行性，炔烃的直接氢酰胺化仍然相当有限。

该文中，该文中报道了一种炔烃与二恶唑酮的氢酰胺化反应的NiH催化策略，该策略允许在（E）-反马尔可夫或马尔可夫选择性中方便地合成有用的二次烯酰胺。该反应对末端和内部炔烃都是可行的，并且对一系列细微的官能团也有耐受性。由于H2O是催化剂高转化率的重要组分，提出了内球类硝基苯转移的参与超过了不希望的半还原过程，从而首次展示了镍催化二恶唑酮形成金属类硝基苯的能力。

附：英文原文

Title: Merging NiH Catalysis and Inner-Sphere Metal-Nitrenoid Transfer for Hydroamidation of Alkynes

Author: Xiang Lyu, Jianbo Zhang, Dongwook Kim, Sangwon Seo, Sukbok Chang

Issue&Volume: April 9, 2021

Abstract: The formal hydroamination/hydroamidation utilizing metal hydride is an appealing synthetic tool for the construction of valuable nitrogen-containing compounds from unsaturated hydrocarbons. While significant advances have been made for the functionalizations of alkenes in this realm, the direct hydroamidation of alkynes remains rather limited due to the high feasibility of the key metal-alkenyl intermediate to choose other reaction pathways. Herein, we report a NiH-catalyzed strategy for the hydroamidation of alkynes with dioxazolones, which allows convenient access to synthetically useful secondary enamides in (E)-anti-Markovnikov or Markovnikov selectivity. The reaction is viable for both terminal and internal alkynes and is also tolerant with a range of subtle functional groups. With H2O found as an essential component for high catalyst turnovers, the involvement of inner-sphere nitrenoid transfer is proposed that outcompetes an undesired semireduction process, thus representing the first example to show the competence of Ni catalysis for metal-nitrenoid formation from dioxazolones.

DOI: 10.1021/jacs.1c01138

Source: https://pubs.acs.org/doi/10.1021/jacs.1c01138