Palladium-Catalyzed Olefin Dioxygenation

A general method for the vicinal dioxygenation of olefins was developed using cationic Pd diphosphine complexes as the catalysts and PhI(OAc)2 as the terminal oxidant. In comparison to known Pd-catalyzed vicinal oxidations, this method is suitable for a broad range of olefins in both inter- and intramolecular reactions. An 18O-labeling experiment provides insight into the mechanism of this transformation which presumably involves Pd(II)/Pd(IV) intermediates.

本研究开发了一种以阳离子钯双膦配合物（cationic Pd diphosphine complexes）为催化剂、二醋酸碘苯（PhI(OAc)2）为末端氧化剂的烯烃（olefins）邻位双氧化通用方法。相较于已报道的钯催化邻位氧化反应，该方法可适用于分子间与分子内两类反应中的广谱烯烃底物。本研究通过氧-18标记实验（18O-labeling experiment）阐明了该转化的反应机理，推测其过程涉及钯(II)/钯(IV)（Pd(II)/Pd(IV)）中间体。