Chen Junjun, Hua Kaimin, Liu Xiaofang, Deng Yuchao, Wei Baiyin, Wang Hui, Sun Yuhan
CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute Chinese Academy of Sciences, Shanghai, 201210, P. R. China.
University of Chinese Academy of Science, Beijing, 100049, P. R. China.
Chemistry. 2021 Jul 7;27(38):9919-9924. doi: 10.1002/chem.202100849. Epub 2021 May 27.
Performing carbonylation without the use of carbon monoxide for high-value-added products is an attractive yet challenging topic in sustainable chemistry. Herein, effective methods for producing linear aldehydes or alcohols selectively with formic acid as both carbon monoxide and hydrogen source have been described. Linear-selective hydroformylation of alkenes proceeds smoothly with up to 88 % yield and >30 regioselectivity in the presence of single Rh catalyst. Strikingly, introducing Ru into the system, the dual Rh/Ru catalysts accomplish efficient and regioselective hydroxymethylation in one pot. The present processes utilizing formic acid as syngas surrogate operate simply under mild condition, which opens a sustainable way for production of linear aldehydes and alcohols without the need for gas cylinders and autoclaves. As formic acid can be readily produced via CO hydrogenation, the protocols represent indirect approaches for chemical valorization of CO .
在不使用一氧化碳的情况下对高附加值产品进行羰基化反应,是可持续化学领域一个引人关注但具有挑战性的课题。本文描述了以甲酸作为一氧化碳和氢源选择性生产直链醛或醇的有效方法。在单一铑催化剂存在下,烯烃的线性选择性氢甲酰化反应顺利进行,产率高达88%,区域选择性大于30。引人注目的是,将钌引入该体系后,双铑/钌催化剂可在一个反应釜中实现高效且区域选择性的羟甲基化反应。目前利用甲酸作为合成气替代物的工艺在温和条件下操作简便,为无需气瓶和高压釜生产直链醛和醇开辟了一条可持续的途径。由于甲酸可通过一氧化碳加氢轻松制备,这些方法代表了一氧化碳化学增值的间接途径。