Liu Chengwei, Szostak Michal
School of Chemistry and Materials Science, Nanjing University of Information Science and Technology, 219 Ningliu Road, Nanjing, Jiangsu 210044 (China).
Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ 07102 (United States).
ChemCatChem. 2021 Dec 7;13(23):4878-4881. doi: 10.1002/cctc.202101206. Epub 2021 Sep 25.
Aryl thioethers are tremendously important motifs in various facets of chemical science. Traditional technologies for the precise assembly of aryl thioethers rely on transition-metal-catalyzed cross-coupling of aryl halides; however, despite the continuous advances, the scope of these methods remains limited. Recently a series of reports has advanced an alternative manifold in which thio(esters) are subject to transition-metal-catalyzed decarbonylation, which (1) permits to exploit ubiquitous carboxylic acids as highly desirable and orthogonal precursors to aryl halides; (2) overcomes the issues of high concentration of thiolate anion leading to catalyst poisoning; (3) enables for novel disconnections not easily available from aryl halides; and (4) introduces new concepts in catalysis.
芳基硫醚是化学科学各个领域极为重要的结构单元。传统的用于精确组装芳基硫醚的技术依赖于过渡金属催化的芳基卤化物交叉偶联反应;然而,尽管不断取得进展,这些方法的适用范围仍然有限。最近一系列报告提出了一种替代方法,其中硫(酯)经历过渡金属催化的脱羰反应,这(1)允许将无处不在的羧酸用作芳基卤化物非常理想且正交的前体;(2)克服了硫醇盐阴离子浓度高导致催化剂中毒的问题;(3)能够实现从芳基卤化物不易获得的新型断键方式;(4)引入了催化方面的新概念。