Department of Chemistry, ZJU-NHU United R&D Center, Zhejiang University, Hangzhou, 310027, China.
State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China.
Chemistry. 2023 Jun 2;29(31):e202300106. doi: 10.1002/chem.202300106. Epub 2023 Apr 21.
The utilization of CO as a non-toxic and cheap feedstock for C1 is a desirable route to achieve high value-added chemicals. In this context, we report a highly efficient ruthenium-catalyzed semi-hydrogenation reaction of CO -derived ureas. Various alkyl and aryl urea derivatives were successfully hydrogenated to obtain the corresponding recyclable amines and formamides (up to 97 % yield), highlighting the good substrate applicability of this method, which makes this method a sustainable alternative for the hydrogenation of CO to formamides in the presence of amines. In the meantime, we have discovered a new pathway that enables rapid hydrogenation of urea derivatives even at lower H pressure (<5 bar). This methodology might provide a new insight into the reduction functionalization of CO under mild pressure to form new C-N bond. Based on the control experiments and the observed intermediate products, we clarify the mechanism for selective semi-hydrogenation of ureas.
将 CO 作为一种无毒且廉价的 C1 原料加以利用，是一条获得高附加值化学品的理想途径。在此背景下，我们报告了一种高效的钌催化的 CO 衍生脲的半氢化反应。各种烷基和芳基脲衍生物被成功氢化，得到相应的可回收的胺和甲酰胺（高达 97%的产率），突出了该方法良好的底物适用性，这使得该方法成为在胺存在下氢化 CO 为甲酰胺的一种可持续替代方法。同时，我们发现了一条新途径，即使在较低的 H2 压力（<5 巴）下，也能使脲衍生物迅速氢化。该方法可能为在温和压力下 CO 的还原官能化形成新的 C-N 键提供新的见解。基于对照实验和观察到的中间产物，我们阐明了脲选择性半氢化的反应机制。
