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