Gold-Catalyzed Intermolecular Formal Insertion of Aryldiazo Esters into Cp-H Bonds of Iron and Ruthenium Metallocenes.

Abstract

The reaction of ferrocene and ruthenocene with aryldiazo acetates in the presence of gold catalysts produced new functionalized metallocenes resulting from a C-H bond functionalization process. This process is believed to proceed through initial decomposition of the diazo component and formation of an electrophilic gold-carbene intermediate, which is subsequently involved in an electrophilic aromatic substitution. The gold-catalyzed functionalization of ruthenocene exhibited a broad scope and a notable functional-group tolerance. Interestingly, the functionalized ferrocene derivatives were found to react with molecular oxygen to yield α-aryl-α-ferrocenyl-α-hydroxyacetates. Adsorption on silica gel was found to be essential for this dioxygen activation/C(sp3 )-H bond functionalization sequence. The methodologies reported herein provide a simple and efficient approach to functionalized metallocene derivatives that are difficult to access through conventional organic functional group transformations.