Liu Zhenghui, Wang Peng, Yan Zhenzhong, Chen Suqing, Yu Dongkun, Zhao Xinhui, Mu Tiancheng
School of Pharmaceutical and Materials Engineering, Taizhou University, Taizhou 318000, Zhejiang, China.
Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Beilstein J Org Chem. 2020 Apr 8;16:645-656. doi: 10.3762/bjoc.16.61. eCollection 2020.
The reductive carbonylation of aryl iodides to aryl aldehydes possesses broad application prospects. We present an efficient and facile Rh-based catalytic system composed of the commercially available Rh salt RhCl·3HO, PPh as phosphine ligand, and EtN as the base, for the synthesis of arylaldehydes via the reductive carbonylation of aryl iodides with CO and H under relatively mild conditions with a broad substrate range affording the products in good to excellent yields. Systematic investigations were carried out to study the experimental parameters. We explored the optimal ratio of Rh salt and PPh ligand, substrate scope, carbonyl source and hydrogen source, and the reaction mechanism. Particularly, a scaled-up experiment indicated that the catalytic method could find valuable applications in industrial productions. The low gas pressure, cheap ligand and low metal dosage could significantly improve the practicability in both chemical researches and industrial applications.
芳基碘化物还原羰基化制备芳基醛具有广阔的应用前景。我们报道了一种高效、简便的铑基催化体系，该体系由市售铑盐RhCl·3H₂O、膦配体三苯基膦（PPh₃）和碱三乙胺（Et₃N）组成，用于在相对温和的条件下通过芳基碘化物与一氧化碳（CO）和氢气（H₂）的还原羰基化反应合成芳基醛，底物范围广泛，产物收率良好至优异。进行了系统研究以考察实验参数。我们探索了铑盐与三苯基膦配体的最佳比例、底物范围、羰基源和氢源以及反应机理。特别地，放大实验表明该催化方法在工业生产中具有重要应用价值。低气压、廉价配体和低金属用量可显著提高其在化学研究和工业应用中的实用性。
