摘要：Shumei Xia,JiaoyuPeng,ShaoleiXie,TaoshanXu, Lijuan Li, Xin Liu, Dawei Cao,* Liang-Nian He,* and Chao-Jun Li*
转自：康龙化成
Copper-Catalyzed Chemoselective Hydrogenation of Unsaturated Bonds with Formic Acid Formateas Hydrogen Donor
Shumei Xia, Jiaoyu Peng, Shaolei Xie,Taoshan Xu, Lijuan Li, Xin Liu, Dawei Cao,* Liang-Nian He,* and Chao-Jun Li*
1 Department of Chemistry, and FRQNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke St. West, Montreal, QC H3A 0B8, Canada;
2 State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. China;
3 Key Laboratory of Green and High-end Utilization of Salt Lake Resources, Qinghai Engineering and Technology Research Center of Comprehensive Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining, Qinghai 810008, China.
—Organic Letters, 2025, doi: 10.1021/jacs.4c15827
Recommended by Depei Meng_MC4
KEY WORDS:Hydrogenation, Cu catalysis (反应类型), alkynes, ketones, aldehydes, and imines (原料), alkene, alcohol, amines (产物), C(sp2)–C(sp2), C(sp3)–O and C(sp3)–N (成键类型), Cu2O, dppp(其他)
ABSTRACT: A novel and sustainable strategy, using earth abundant Cu2O as catalyst and biorenewable HCOOH/HCOOK as hydrogen donor for the efficient hydrogenation of multiple unsaturated compounds, including internal and terminal alkynes, ketones, aldehydes, and imines, has been developed to access high-value chemicals with high chemoselectivity. This protocol features operation simplicity, wide substrate applicability, and only CO2as a byproduct. Additionally, gram-scale experiments and the modification of biologically active molecules all exemplified the synthetic versatility of this protocol.
Strategies for hydrogenation of unsaturated bonds and optimization
Substrate scope of internal alkynes
Substrate scope of imines,ketones, and aldehydes
Applications of the hydrogenation of unsaturated bonds
In conclusion, Shumei Xia et al.have demonstrated that a novel combination of an earth-abundant and operationally simple Cu2O-catalyst and commercially availableHCOOH/HCOOK as hydrogen sourcescan efficiently achieve the hydrogenation of a broad range of unsaturated compounds, including both internal and terminal alkynes, ketones, aldehydes, and imines. The strong versatility, operational simplicity, high chemoselectivity, and excellent functional group tolerance make this system a sustainable and practical strategy to prepare various hydrogenated chemicals, such as internal and terminal alkenes, primary and second alcohols and amines. These easy-tooperate and remarkable hydrogenation conversions are anticipated to be applied in fine chemical synthesis and materials science.
总地来说，Shumei Xia等报道了一种以廉价易得的Cu2O作为催化剂，市售的HCOOH/HCOK作为氢源的新型组合体系，可以实现包括内部和末端的炔烃、酮、醛和亚胺在内的各种不饱和化合物的氢化。该系统凭借其强大的普适性、操作简便性、高化学选择性以及优异的官能团耐受性，成为制备内烯烃、端烯烃、伯醇、仲醇及胺类等氢化产物的可持续实用策略。这些操作简便且效果显著的氢化转化技术有望应用于精细化学品合成和材料科学领域。
来源：新浪财经
