A Computational Study on the Mechanism of Catalytic Cyclopropanation Reaction with Cobalt N-Confused Porphyrin: The Effects of Inner Carbon and Intramolecular Axial Ligand.

The factors that affect acceleration and high / selectivity in the catalytic cyclopropanation reaction of styrene with ethyl diazoacetate by cobalt N-confused porphyrin (NCP) complexes were investigated using density functional theory calculations. The reaction rate was primarily related to the energy gap between the cobalt-carbene adduct intermediates, and , which was affected by the NCP skeletons and axial pyridine ligands more than the corresponding porphyrin complex. In addition, high / stereoselectivity was determined at the and, in part, in the isomerization process at the carbon-centered radical intermediates, and .