Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen (Germany) http://www.schoenebeck.oc.rwth-aachen.de/
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen (Germany) http://www.schoenebeck.oc.rwth-aachen.de/.
Angew Chem Int Ed Engl. 2015 Jun 1;54(23):6809-13. doi: 10.1002/anie.201501617. Epub 2015 Apr 27.
While palladium catalysis is ubiquitous in modern chemical research, the recovery of the active transition-metal complex under routine laboratory applications is frequently challenging. Described herein is the concept of alternative cross-coupling cycles with a more robust (air-, moisture-, and thermally-stable) dinuclear Pd(I) complex, thus avoiding the handling of sensitive Pd(0) species or ligands. Highly efficient C-SCF3 coupling of a range of aryl iodides and bromides was achieved, and the recovery of the Pd(I) complex was accomplished via simple open-atmosphere column chromatography. Kinetic and computational data support the feasibility of dinuclear Pd(I) catalysis. A novel SCF3-bridged Pd(I) dimer was isolated, characterized by X-ray crystallography, and verified to be a competent catalytic intermediate.
虽然钯催化在现代化学研究中无处不在，但在常规实验室应用中回收活性过渡金属配合物常常具有挑战性。本文描述了具有更稳定（耐空气、水分和热）双核 Pd(I)配合物的替代交叉偶联循环的概念，从而避免了处理敏感的 Pd(0)物种或配体。通过简单的开放空气柱层析，实现了一系列芳基碘化物和溴化物的高效 C-SCF3 偶联，并且通过简单的开放空气柱层析完成了 Pd(I)配合物的回收。动力学和计算数据支持双核 Pd(I)催化的可行性。分离出了一种新型的 SCF3 桥联 Pd(I)二聚体，通过 X 射线晶体学进行了表征，并验证为一种有效的催化中间体。
