Fang Xianjie, Yu Peng, Prina Cerai Gabriele, Morandi Bill
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany.
Chemistry. 2016 Oct 24;22(44):15629-15633. doi: 10.1002/chem.201604061. Epub 2016 Sep 23.
A new transfer hydrofunctionalization strategy to turnover H-M -X complexes has enabled both intra- and intermolecular Mizoroki-Heck (MH)-type reactions of aryl cyanides that are challenging to realize under traditional, basic conditions. Initially, a cascade carbonickelation/MH reaction of 2-cyanostyrenes was achieved using a key alkyne transfer hydrocyanation step. Mechanistic experiments supported the proposed catalytic cycle, including the turnover-enabling transfer hydrocyanation step. The reactivity was then extended to the intermolecular MH reaction of benzonitriles and styrenes.
一种用于使H-M-X配合物发生周转的新型转移氢官能团化策略,实现了芳基腈的分子内和分子间Mizoroki-Heck(MH)型反应,而这些反应在传统碱性条件下很难实现。最初,通过关键的炔烃转移氢氰化步骤,实现了2-氰基苯乙烯的串联碳镍化/MH反应。机理实验支持了所提出的催化循环,包括使反应发生周转的转移氢氰化步骤。随后,该反应活性扩展到了苯甲腈和苯乙烯的分子间MH反应。