Liu Jie, Zheng Hong-Xing, Yao Chuan-Zhi, Sun Bing-Feng, Kang Yan-Biao
Center of Advanced Nanocatalysis, Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, China.
J Am Chem Soc. 2016 Mar 16;138(10):3294-7. doi: 10.1021/jacs.6b00180. Epub 2016 Mar 7.
A pharmaceutical-oriented, transition-metal-free, cyanide-free one-step direct transformation of methylarenes to aryl nitriles is described. For the dimethylarenes, the selectivity can be well-controlled to form mononitriles or dinitriles. Enantioenriched nitriles can also be synthesized by this method. As a pharmaceutically practical method, the antidepressant drug citalopram was synthesized from cheap and commercially abundant m-xylene on a gram scale in high yield, avoiding transition-metal residues and toxic cyanides.
本文描述了一种以药物为导向、无过渡金属、无氰化物的甲基芳烃一步直接转化为芳腈的方法。对于二甲苯类化合物，选择性可以得到很好的控制，以形成单腈或二腈。通过该方法还可以合成对映体富集的腈。作为一种具有药物实用性的方法，以廉价且商业可得的间二甲苯为原料，以高收率克级规模合成了抗抑郁药物西酞普兰，避免了过渡金属残留和有毒氰化物。
