New approach to the air oxidation of alkenes employing metal nitro complexes as catalysts
Alkenes are stoichiometrically and, in the presence of air, catalytically oxidized by cis-bis(aceto-nitrile) chloronitropalladium(II). Oxidation of monosubstituted terminal alkenes and trans-cyclooctene yields the corresponding ketone, oxidation of cyclopentene and cyclohexene the corresponding allyl alcohol, and oxidation of bicyclic alkenes the corresponding epoxide, each with good selectivity for the respective product. Other alkenes give varying mixtures of the above products together with, in some cases, the ..cap alpha..,..beta..-unsaturated ketone. Vinyl ethers yield the corresponding ester while (trimethylsily)ethylene yields (trimethylsilyl)acetaldehyde. The selectivities are rationalized on the basis of ease of ..beta..-hydrogen elimination in observed intermediate heterometallacyclopentane complexes formed by nucleophilic attack of the nitro oxygen atom on the coordinated alkene in alkene nitro complexes. The general role of metallacycles in metal-mediated alkene oxidations and the advantages and disadvantages of intra-vs. intermolecular metal nitro catalyzed alkene oxidations are discussed. 50 references, 4 figures, 3 tables.
- Research Organization:
- Brookhaven National Lab., Upton, NY
- OSTI ID:
- 5103122
- Journal Information:
- Organometallics; (United States), Vol. 3:12
- Country of Publication:
- United States
- Language:
- English
Similar Records
Alkene epoxidations catalyzed by iron(III), manganese(III), and chromium(III) porphyrins. Effects of metal and porphyrin substituents on selectivity and regiochemistry of epoxidation
Reactions of atomic carbon with oxygenated compounds and the investigation of fullerene chemistry
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKENES
OXIDATION
NITROGEN COMPLEXES
CATALYTIC EFFECTS
CATALYSIS
PALLADIUM COMPLEXES
AIR
CATALYSTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
EXPERIMENTAL DATA
REACTION INTERMEDIATES
CHEMICAL REACTIONS
COMPLEXES
DATA
FLUIDS
GASES
HYDROCARBONS
INFORMATION
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES
YIELDS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)