Xu Caiyun, Wu Haihong, Zhang Zhanrong, Zheng Bingxiao, Zhai Jianxin, Zhang Kaili, Wu Wei, Mei Xuelei, He Mingyuan, Han Buxing
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University Shanghai 200062 China
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences Beijing 100190 China
Chem Sci. 2022 Jan 19;13(6):1629-1635. doi: 10.1039/d1sc06430d. eCollection 2022 Feb 9.
Effective hydrodeoxygenation (HDO) of aromatic alcohols is very attractive in both conventional organic synthesis and upgrading of biomass-derived molecules, but the selectivity of this reaction is usually low because of the competitive hydrogenation of the unsaturated aromatic ring and the hydroxyl group. The high activity of noble metal-based catalysts often leads to undesired side reactions (, saturation of the aromatic ring) and excessive hydrogen consumption. Non-noble metal-based catalysts suffer from unsatisfied activity and selectivity and often require harsh reaction conditions. Herein, for the first time, we report chemoselective HDO of various aromatic alcohols with excellent selectivity, using porous carbon-nitrogen hybrid material-supported Co catalysts. The C-OH bonds were selectively cleaved while leaving the aromatic moiety intact, and in most cases the yields of targeted compounds reached above 99% and the catalyst could be readily recycled. Nitrogen doping on the carbon skeleton of the catalyst support (C-N matrix) significantly improved the yield of the targeted product. The presence of large pores and a high surface area also improved the catalyst efficiency. This work opens the way for efficient and selective HDO reactions of aromatic alcohols using non-noble metal catalysts.
芳香醇的高效加氢脱氧(HDO)在传统有机合成以及生物质衍生分子的升级过程中都极具吸引力,但由于不饱和芳环和羟基的竞争性氢化作用,该反应的选择性通常较低。基于贵金属的催化剂活性高,常常导致不期望的副反应(如芳环饱和)以及过度的氢气消耗。基于非贵金属的催化剂则存在活性和选择性不尽人意的问题,且通常需要苛刻的反应条件。在此,我们首次报道了使用多孔碳氮杂化材料负载的钴催化剂,对各种芳香醇进行具有优异选择性的化学选择性HDO反应。C-OH键被选择性裂解,而芳基部分保持完整,在大多数情况下,目标化合物的产率达到99%以上,且催化剂可轻松回收。在催化剂载体的碳骨架(C-N基质)上进行氮掺杂显著提高了目标产物的产率。大孔和高比表面积的存在也提高了催化剂效率。这项工作为使用非贵金属催化剂高效、选择性地进行芳香醇的HDO反应开辟了道路。