Cyclohexene as a substrate probe for the nature of the high-valent iron-oxo oxidant in Fe(TPA)-catalyzed oxidations
作者： Williamson N. Oloo , Yan Feng , Shyam Iyer , Sean Parmelee , Genqiang Xue
DOI: 10.1039/C3NJ00524K
关键词: Cyclohexene 、 Photochemistry 、 Amine gas treating 、 Chemistry 、 Epoxide 、 Selectivity 、 Catalysis 、 High-valent iron 、 Medicinal chemistry 、 Substrate (chemistry) 、 Allylic rearrangement
摘要: Cyclohexene is shown to be a versatile substrate probe in shedding light on the nature of high-valent oxidant generated by bio-inspired nonheme iron catalysts. provides choice attack an allylic C–H bond or CC bond, and selectivity observed should depend electronic properties oxidant. Allylic oxidation products are predominantly reaction with [FeIV(O)(TPA)(NCCH3)]2+ (TPA = tris(2-pyridylmethyl)amine), while epoxide cis-diol major found [FeII(TPA)(NCCH3)2]2+-catalyzed H2O2. This difference suggests that latter case must distinct from supports oxoiron(V)-hydroxo species has been proposed as
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M. H. Lim, J.-U. Rohde, A. Stubna, M. R. Bukowski, M. Costas, R. Y. N. Ho, E. Munck, W. Nam, L. Que, An FeIV=O complex of a tetradentate tripodal nonheme ligand. Proceedings of the National Academy of Sciences of the United States of America. ,vol. 100, pp. 3665- 3670 ,(2003) , 10.1073/PNAS.0636830100
Miquel Costas, Mark P. Mehn, Michael P. Jensen, Lawrence Que, Dioxygen Activation at Mononuclear Nonheme Iron Active Sites: Enzymes, Models, and Intermediates Chemical Reviews. ,vol. 104, pp. 939- 986 ,(2004) , 10.1021/CR020628N
Lawrence Que, William B. Tolman, Biologically inspired oxidation catalysis Nature. ,vol. 455, pp. 333- 340 ,(2008) , 10.1038/NATURE07371
Oleg Y. Lyakin, Konstantin P. Bryliakov, George J. P. Britovsek, Evgenii P. Talsi, EPR spectroscopic trapping of the active species of nonheme iron-catalyzed oxidation. Journal of the American Chemical Society. ,vol. 131, pp. 10798- 10799 ,(2009) , 10.1021/JA902659C
John T. Groves, Robert C. Haushalter, Mikio Nakamura, Thomas E. Nemo, B. J. Evans, High-valent iron-porphyrin complexes related to peroxidase and cytochrome P-450 Journal of the American Chemical Society. ,vol. 103, pp. 2884- 2886 ,(1981) , 10.1021/JA00400A075
James E. Penner-Hahn, Kim. Smith Eble, Thomas J. McMurry, Mark. Renner, Alan L. Balch, John T. Groves, John H. Dawson, Keith O. Hodgson, Structural characterization of horseradish peroxidase using EXAFS spectroscopy: evidence for Fe=O ligation in compounds I and II Journal of the American Chemical Society. ,vol. 108, pp. 7819- 7825 ,(1986) , 10.1021/JA00284A054
Dainius Macikenas, Ewa Skrzypczak-Jankun, John D. Protasiewicz, A New Class of Iodonium Ylides Engineered as Soluble Primary Oxo and Nitrene Sources Journal of the American Chemical Society. ,vol. 121, pp. 7164- 7165 ,(1999) , 10.1021/JA200554V
Peter Comba, Gopalan Rajaraman, Heidi Rohwer, A Density Functional Theory Study of the Reaction of the Biomimetic Iron(II) Complex of a Tetradentate Bispidine Ligand with H2O2 Inorganic Chemistry. ,vol. 46, pp. 3826- 3838 ,(2007) , 10.1021/IC061129Y
Rubén Mas-Ballesté, Lawrence Que, Iron-catalyzed olefin epoxidation in the presence of acetic acid: insights into the nature of the metal-based oxidant. Journal of the American Chemical Society. ,vol. 129, pp. 15964- 15972 ,(2007) , 10.1021/JA075115I
Andrea Decker, Jan-Uwe Rohde, Eric J. Klinker, Shaun D. Wong, Lawrence Que,, Edward I. Solomon, Spectroscopic and quantum chemical studies on low-spin FeIV=O complexes: Fe-O bonding and its contributions to reactivity. Journal of the American Chemical Society. ,vol. 129, pp. 15983- 15996 ,(2007) , 10.1021/JA074900S