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First Direct Evidence for Stereospecific Olefin Epoxidation and Alkane Hydroxylation by an Oxoiron(IV) Porphyrin Complex

Title
First Direct Evidence for Stereospecific Olefin Epoxidation and Alkane Hydroxylation by an Oxoiron(IV) Porphyrin Complex
Authors
Nam W.Park S.-E.Lim I.K.Lim M.H.Hong J.Kim J.
Ewha Authors
남원우
SCOPUS Author ID
남원우scopus
Issue Date
2003
Journal Title
Journal of the American Chemical Society
ISSN
0002-7863JCR Link
Citation
vol. 125, no. 48, pp. 14674 - 14675
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
We report in this study that an oxoiron(IV) porphyrin complex bearing electron-deficient porphyrin ligand, (TPFPP)FeIV=O (TPFPP = meso-tetrakis(pentafluorophenyl)porphinato dianion), shows reactivities similar to those found in oxoiron(IV) porphyrin π-cation radicals. In the epoxidation of olefins by the (TPFPP)FeIV=O complex, epoxides were yielded as major products; cyclohexene oxide was the sole product formed in the epoxidation of cyclohexene, and stilbenes were stereospecifically oxidized to the corresponding epoxide products. More striking results were obtained in alkane hydroxylation reactions; the hydroxylation of adamantane afforded a high degree of selectivity for tertiary C?H bonds over secondary C?H bonds, and the hydroxylation of cis-1,2-dimethylcyclohexane yielded a tertiary alcohol product with >99% retention of stereochemistry. The latter result demonstrates that an oxoiron(IV) porphyrin complex hydroxylates alkanes with a high stereospecificity. Isotope labeling studies performed with H218O and 18O2 in the olefin epoxidation and alkane hydroxylation reactions demonstrated that oxygen atoms in oxygenated products derived from the oxoiron(IV) porphyrin complex. Copyright © 2003 American Chemical Society.
DOI
10.1021/ja0368204
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자연과학대학 > 화학·나노과학전공 > Journal papers
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