Studies of iron-mediated Pauson–Khand reactions of 1,1-disubstituted-allenylsilanes: mechanistic implications for a reactive three-membered iron metallacycle

Abstract

Pauson–Khand reactions of 1,1-disubstituted allenylsilanes have been explored using diiron nonacarbonyl. These studies describe the characterization of three-membered iron metallacycles as reaction-competent intermediates leading to stereoselective formation of highly functionalized 4-alkylidene-2-cyclopenten-1-ones. Studies of the reaction profile provide insights leading to the proposal of a stereoselective mechanistic pathway, which has not been previously explored. Furthermore, these reactions have been examined using computational chemistry, and these efforts have detailed the unique behavior of Fe(CO)₄ and its role in Pauson–Khand processes.