College of Materials Science and Opto-Electronic Technology &, Center of Materials Science and Optoelectronics Engineering &, CAS Center for Excellence in Topological Quantum Computation &, CAS Key Laboratory of Vacuum Physic, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Department of Neurosurgery & Health Science Center Shenzhen Second People's Hospital, The First Affiliated Hospital Shenzhen University, Shenzhen, 518035, P. R. China.
Chemistry. 2022 Jun 21;28(35):e202200869. doi: 10.1002/chem.202200869. Epub 2022 May 11.
Aryl sulfides are in great demands in drugs and materials sciences. To avoid using nucleophilic and noxious thiols, many efforts have been focused on exploring novel sulfide resources. Herein, a reductive Pd-catalyzed, Ni-mediated method to synthesize aryl sulfides via a sulfide transfer reaction is developed. The utility and scope of this reaction is exemplified by various aryl electrophiles and aryl sulfides. Mechanistic studies reveal two competing catalytic cycles of sulfide transfer and aryl transfer in this reaction, where the former one is favored over the later one because of the large energy barrier difference during the transmetalation. Moreover, two important chemicals are late-stage functionalized by this method, exhibiting the potential applications in drugs and materials science.
芳基硫醚在药物和材料科学中需求量很大。为避免使用亲核性和有毒的硫醇，人们已经投入了很多努力来探索新型的硫化物资源。在此，我们开发了一种通过硫转移反应合成芳基硫醚的还原 Pd 催化、Ni 介导的方法。该反应通过各种芳基亲电试剂和芳基硫醚证明了其通用性和适用范围。机理研究表明，在该反应中存在两种竞争的硫转移和芳基转移催化循环，由于在转金属化过程中能量垒差异较大，前者优先于后者。此外，该方法还对两种重要的化学物质进行了后期功能化，展示了在药物和材料科学中的潜在应用。
