Olefin synthesis by vanadium(V)-induced oxidative decarboxylation-deoxygenation of 3-hydroxy carboxylic acids

Journal Article · Fri Oct 12 00:00:00 EDT 1990 · Journal of Organic Chemistry; (United States)

DOI:https://doi.org/10.1021/jo00308a021· OSTI ID:5148489

Meier, I K; Schwartz, J ^[1]

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1. Princeton Univ., NJ (United States)

Oxidative decarboxylation of 3-hydroxy carboxylic acids can be effected with various V(V) complexes. This process likely yields an intermediate 1,4-metalla diradical. {beta}-elimination from this intermediate gives olefin and regenerates V(V), likely as VO{sub 2}Cl. Thus, although the overall process involves no net change in oxidation state for vanadium, the decarboxylation process is oxidatively induced. Intramolecular trapping of the intermediate yields glycolate and then C-C cleavage products, and skeletal rearrangement gives ketonic products. Qualitatively, rates for oxidative decarboxylation of the acids and the stereospecificity of formation of olefinic products depend on the electron-withdrawing ability of groups attached to vanadium. Methodology is described for the preparation of tri- and tetrasubstituted olefins in high yield from appropriate 3-hydroxy carboxylic acid precursors.

• OSTI ID: 5148489
• Journal Information: Journal of Organic Chemistry; (United States), Journal Name: Journal of Organic Chemistry; (United States) Vol. 55:21; ISSN JOCEA; ISSN 0022-3263
• Country of Publication: United States
• Language: English

Related Subjects

10 SYNTHETIC FUELS
100200* -- Synthetic Fuels-- Production-- (1990-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
ADSORBENTS
ALDEHYDES
ALKENES
BENZALDEHYDE
CARBOXYLIC ACIDS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHROMATOGRAPHY
COHERENT SCATTERING
COMPLEXES
DECARBOXYLATION
DIFFRACTION
GAS CHROMATOGRAPHY
HYDROCARBONS
HYDROGEN COMPOUNDS
INORGANIC ACIDS
LEWIS ACIDS
LIQUID COLUMN CHROMATOGRAPHY
MASS SPECTROSCOPY
MOLECULAR STRUCTURE
NMR SPECTRA
ORGANIC ACIDS
ORGANIC COMPOUNDS
OXIDATION
RADICALS
REACTION INTERMEDIATES
SCATTERING
SEPARATION PROCESSES
SILICA GEL
SPECTRA
SPECTROSCOPY
STEREOCHEMISTRY
SYNTHESIS
THIN-LAYER CHROMATOGRAPHY
TRANSITION ELEMENT COMPLEXES
VANADIUM COMPLEXES
X-RAY DIFFRACTION