ON THE MECHANISM OF OXYGEN INSERTION CATALYZED BY CYTOCHROME P-450. HYDROXYLATION WITH PARTIAL ALLYLIC REARRANGEMENT

Autor: Oluwamuye F. Akinbote, John T. Groves, Guillermina E. Avaria
Rok vydání: 1980
Předmět:
DOI: 10.1016/b978-0-12-187701-9.50050-4
Popis: The cumene hydroperoxide dependent oxidation of cyclohexene catalyzed cytochrome P-450 produced cyclohexene oxide and cyclohexenol. Catalytic Systems containing chlorotetraphenyl-porphinatoiron(III)-iodosylbenzene and chlorotetraphenylpor-phinatochromium (III)-iodosylbenzene gave the same products. The oxidation of 1,2-dideuterocyclohexene by these systems gave cyclohexenol with various degrees of allylic rearrangement. With the chromium catalyst nearly complete, allylic scrambling was observed whereas the iron catalyst and cytochrome P-450 gave only partial equilibration. A mechanism involving caged radical intermediates is presented to account for these results.
Databáze: OpenAIRE