TY - JOUR
T1 - Olefin cis-dihydroxylation with bio-inspired iron catalysts. evidence for an FeII/FeIV catalytic cycle
AU - Oldenburg, Paul D.
AU - Feng, Yan
AU - Pryjomska-Ray, Iweta
AU - Ness, Daniel
AU - Que, Lawrence
PY - 2010/12/22
Y1 - 2010/12/22
N2 - Iron(II) complexes of a series of N-acylated dipyridin-2-ylmethylamine ligands (R-DPAH) have been investigated as catalysts for the cis-dihydroxylation of olefins to model the action of Rieske dioxygenases that catalyze arene cis-dihydroxylation. The Rieske dioxygenases have a mononuclear iron active site coordinated to a 2-histidine-1-carboxylate facial triad motif. The R-DPAH ligands are designed to provide a facial N,N,O-ligand set that mimics the enzyme active site. The iron(II) complexes of the R-DPAH ligands activate H 2O2 to effect the oxidation of olefin substrates into cis-diol products. As much as 90% of the H2O2 oxidant is converted into cis-diol, but a large excess of olefin is required to achieve the high conversion efficiency. Reactivity and mechanistic comparisons with the previously characterized Fe(TPA)/H2O2 catalyst/oxidant combination (TPA = tris(pyridin-2-ylmethyl)amine) lead us to postulate an FeII/FeIV redox cycle for the Fe(R-DPAH) catalysts in which an FeIV(OH)2 oxidant carries out the cis-hydroxylation of olefins. This hypothesis is supported by three sets of observations: (a) the absence of a lag phase in the conversion of the H 2O2 oxidant into a cis-diol product, thereby excluding the prior oxidation of the Fe(II) catalyst to an Fe(III) derivative as established for the Fe(TPA) catalyst; (b) the incorporation of H218O into the cis-diol product, thereby requiring O-O bond cleavage to occur prior to cis-diol formation; and (c) the formation of cis-diol as the major product of cyclohexene oxidation, rather than the epoxide or allylic alcohol products more commonly observed in metal-catalyzed oxidations of cyclohexene, implicating an oxidant less prone to oxo transfer or H-atom abstraction.
AB - Iron(II) complexes of a series of N-acylated dipyridin-2-ylmethylamine ligands (R-DPAH) have been investigated as catalysts for the cis-dihydroxylation of olefins to model the action of Rieske dioxygenases that catalyze arene cis-dihydroxylation. The Rieske dioxygenases have a mononuclear iron active site coordinated to a 2-histidine-1-carboxylate facial triad motif. The R-DPAH ligands are designed to provide a facial N,N,O-ligand set that mimics the enzyme active site. The iron(II) complexes of the R-DPAH ligands activate H 2O2 to effect the oxidation of olefin substrates into cis-diol products. As much as 90% of the H2O2 oxidant is converted into cis-diol, but a large excess of olefin is required to achieve the high conversion efficiency. Reactivity and mechanistic comparisons with the previously characterized Fe(TPA)/H2O2 catalyst/oxidant combination (TPA = tris(pyridin-2-ylmethyl)amine) lead us to postulate an FeII/FeIV redox cycle for the Fe(R-DPAH) catalysts in which an FeIV(OH)2 oxidant carries out the cis-hydroxylation of olefins. This hypothesis is supported by three sets of observations: (a) the absence of a lag phase in the conversion of the H 2O2 oxidant into a cis-diol product, thereby excluding the prior oxidation of the Fe(II) catalyst to an Fe(III) derivative as established for the Fe(TPA) catalyst; (b) the incorporation of H218O into the cis-diol product, thereby requiring O-O bond cleavage to occur prior to cis-diol formation; and (c) the formation of cis-diol as the major product of cyclohexene oxidation, rather than the epoxide or allylic alcohol products more commonly observed in metal-catalyzed oxidations of cyclohexene, implicating an oxidant less prone to oxo transfer or H-atom abstraction.
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U2 - 10.1021/ja1021014
DO - 10.1021/ja1021014
M3 - Article
C2 - 21105649
AN - SCOPUS:78650288060
SN - 0002-7863
VL - 132
SP - 17713
EP - 17723
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 50
ER -