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 trans/cis 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...

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Bibliographic Details
Published in:Molecules (Basel, Switzerland) Switzerland), 2022-10, Vol.27 (21), p.7266
Main Authors: Iwanaga, Osamu, Miyanishi, Mayuko, Tachibana, Toshihiro, Miyazaki, Takaaki, Shiota, Yoshihito, Yoshizawa, Kazunari, Furuta, Hiroyuki
Format: Article
Language:English
Subjects:
Acceleration
acceleration effect
Carbon
Cobalt
Computer applications
cyclopropanation reaction
Cyclopropane compounds
Density functional theory
Density functionals
Energy
Intermediates
Isomerization
Ligands
N-confused porphyrin
Porphyrins
Pyridine
Selectivity
Stereoselectivity
Styrene
theoretical calculation
trans/cis selectivity
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Summary:The factors that affect acceleration and high trans/cis 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, A and B, which was affected by the NCP skeletons and axial pyridine ligands more than the corresponding porphyrin complex. In addition, high trans/cis stereoselectivity was determined at the TS1 and, in part, in the isomerization process at the carbon-centered radical intermediates, Ctrans and Ccis.
ISSN:1420-3049
1420-3049
DOI:10.3390/molecules27217266