Scattolin Thomas, Senol Erdem, Yin Guoyin, Guo Qianqian, Schoenebeck Franziska
Institute of Organic Chemistry, RWTH Aachen University, Aachen, Germany.
Institute of Inorganic Chemistry, X-ray Crystallography, Landoltweg 1, 52074, Aachen, Germany.
Angew Chem Int Ed Engl. 2018 Sep 17;57(38):12425-12429. doi: 10.1002/anie.201806036. Epub 2018 Aug 20.
This report widens the repertoire of emerging Pd catalysis to carbon-heteroatom, that is, C-S bond formation. While Pd -catalyzed protocols may suffer from the formation of poisonous sulfide-bound off-cycle intermediates and lack of selectivity, the mechanistically diverse Pd catalysis concept circumvents these challenges and allows for C-S bond formation (S-aryl and S-alkyl) of a wide range of aryl halides. Site-selective thiolations of C-Br sites in the presence of C-Cl and C-OTf were achieved in a general and a priori predictable fashion. Computational, spectroscopic, X-ray, and reactivity data support dinuclear Pd catalysis to be operative. Contrary to air-sensitive Pd , the active Pd species was easily recovered in the open atmosphere and subjected to multiple rounds of recycling.
本报告将新兴的钯催化范围扩展至碳-杂原子，即碳-硫键的形成。虽然钯催化方案可能会因形成有毒的硫醚键非循环中间体以及缺乏选择性而受到影响，但机理多样的钯催化概念克服了这些挑战，并能实现多种芳基卤化物的碳-硫键形成（硫芳基和硫烷基）。在碳-氯和碳-三氟甲磺酸酯存在的情况下，以通用且可预先预测的方式实现了碳-溴位点的位点选择性硫醇化。计算、光谱、X射线和反应性数据支持双核钯催化起作用。与对空气敏感的钯不同，活性钯物种在开放大气中易于回收，并可进行多轮循环利用。
