Biomimetic oxidation with molecular oxygen. Selective carbon-carbon bond cleavage of 1,2-diols by molecular oxygen and dihydropyridine in the presence of iron-porphyrin catalysts
The selective carbon-carbon bond cleavage of 1,2-diols in the presence of an iron-porphyrin complex, molecular oxygen, and 1-benzyl-3-carbamoyl-1,4-dihydropyridine is reported. The C-C bonds of aryl-substituted ethane-1,2-diols were cleaved exclusively to aldehydes or ketones as the oxidation products at room temperature. The reaction rates were influenced by the steric hindrance of the substituents both in the catalysts and diols, but no differences in the reactivities were observed between the two stereo isomers (meso and dl) of diols. A kinetic analysis of this bond cleavage reaction is consistent with the reaction mechanism consisting of the initial binding of diol on the active catalyst forming an intermediate complex and its subsequent breakdown in the rate-determining step of the catalytic cycle. The initial binding step is favorable for electron-deficient diols and is influenced by steric hindrance, whereas the rate-determining bond cleavage step is accelerated by electron-rich diols and unaffected by the steric effect. The mechanism of this diol cleavage reaction is discussed on the basis of these observations.
- Research Organization:
- Kyoto Univ., Japan
- OSTI ID:
- 5419463
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:4; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ALCOHOLS
AZINES
CARBON
CARBOXYLIC ACIDS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
ELEMENTS
EXPERIMENTAL DATA
GLYCOLS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
IRON COMPLEXES
KINETICS
MEDIUM TEMPERATURE
NONMETALS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
OXYGEN
PORPHYRINS
PYRIDINES
REACTION KINETICS
STEREOCHEMISTRY
TRANSITION ELEMENT COMPLEXES