Cation radical probes. Development and application to metalloporphyrin-catalyzed epoxidation

Journal Article · Wed Dec 30 04:00:00 EST 1992 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00053a047· OSTI ID:6201656

Mirafzal, G A; Kim, Taisun; Liu, Jianping; Bauld, N L ^[1]

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1. Univ. of Texas, Austin (United States)

Radical probes such as the cyclization of the 5-hexenyl radical have proved highly effective in diagnosing free radical mechanisms. Analogous cation radical probes would constitute a powerful tool for detecting short-lived cation radical intermediates in the burgeoning area of hole catalytic chemistry. The synthesis of conveniently accessible cation radical probe substrates and the characterization and calibration of their rapid intramolecular probe reactions as cation radical clocks are now reported. The new probes have further been used to investigate the hypothetical electron-transfer mechanism for metalloporphyrin-catalyzed epoxidation. The cation radical probe reactions developed in this study are based upon the intramolecular cation radical Diels-Alder reaction and analogous intramolecular cyclobutanation. 14 refs.

• OSTI ID: 6201656
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 114:27; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBOXYLIC ACIDS
CATALYSIS
CATALYTIC EFFECTS
CATIONS
CHARGED PARTICLES
CHEMICAL ANALYSIS
CHEMICAL REACTIONS
COMPLEXES
DETECTION
DIELS-ALDER REACTION
ELECTRON TRANSFER
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HOMOGENEOUS CATALYSIS
IONS
IRON COMPLEXES
MANGANESE COMPLEXES
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PORPHYRINS
PROBES
QUALITATIVE CHEMICAL ANALYSIS
RADICALS
REACTION INTERMEDIATES
SUBSTRATES
TRANSITION ELEMENT COMPLEXES