Pd-catalyzed oxidative coupling reaction was of great importance in the aromatic C--H activation and the for-mation of new C-O and C--C bonds. Sanford has pioneered practical, directed C-H activation reactions em-ploy...Pd-catalyzed oxidative coupling reaction was of great importance in the aromatic C--H activation and the for-mation of new C-O and C--C bonds. Sanford has pioneered practical, directed C-H activation reactions em-ploying Pd（OAc）2 as catalyst since 2004. However, until now, the speculated reactive Pd（Ⅳ） transient intermedi-ates in these reactions have not been isolated or directly detected from reaction solution. Electrospray ionization tandem mass spectrometry （ESI-MS/MS） was used to intercept and characterize the reactive Pd（Ⅳ） transient inter-mediates in the solutions of Pd（OAc）2-catalyzed oxidative coupling reactions. In this study, the Pd（IV） transient in-termediates were detected from the solution of Pd（OAc）2-catalyzed oxidative coupling reactions by ESI-MS and the MS/MS of the intercepted Pd（IV） transient intermediate in reaction system was the same with the synthesized au-thentic Pd（Ⅳ） complex. Our ESI-MS（/MS） studies confirmed the presence of Pd（Ⅳ） reaction transient intermedi-ates. Most interestingly, the MS/MS of Pd（Ⅳ） transient intermediates showed the reductive elimination reactivity to Pd（Ⅱ） complexes with new C-O bond formation into product in gas phase, which was consistent with the proposed reactivity of the Pd（Ⅳ） transient intermediates in solution.展开更多
文摘Pd-catalyzed oxidative coupling reaction was of great importance in the aromatic C--H activation and the for-mation of new C-O and C--C bonds. Sanford has pioneered practical, directed C-H activation reactions em-ploying Pd（OAc）2 as catalyst since 2004. However, until now, the speculated reactive Pd（Ⅳ） transient intermedi-ates in these reactions have not been isolated or directly detected from reaction solution. Electrospray ionization tandem mass spectrometry （ESI-MS/MS） was used to intercept and characterize the reactive Pd（Ⅳ） transient inter-mediates in the solutions of Pd（OAc）2-catalyzed oxidative coupling reactions. In this study, the Pd（IV） transient in-termediates were detected from the solution of Pd（OAc）2-catalyzed oxidative coupling reactions by ESI-MS and the MS/MS of the intercepted Pd（IV） transient intermediate in reaction system was the same with the synthesized au-thentic Pd（Ⅳ） complex. Our ESI-MS（/MS） studies confirmed the presence of Pd（Ⅳ） reaction transient intermedi-ates. Most interestingly, the MS/MS of Pd（Ⅳ） transient intermediates showed the reductive elimination reactivity to Pd（Ⅱ） complexes with new C-O bond formation into product in gas phase, which was consistent with the proposed reactivity of the Pd（Ⅳ） transient intermediates in solution.
