Low‐Spin and High‐Spin Perferryl Intermediates in Non‐Heme Iron Catalyzed Oxidations of Aliphatic C–H Groups Full article
| Journal |
Chemistry - A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765 |
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| Output data | Year: 2021, Volume: 27, Number: 28, Pages: 7781-7788 Pages count : 8 DOI: 10.1002/chem.202004395 | ||
| Tags | biomimetic chemistry; iron; intermediate; oxidation; selectivity | ||
| Authors |
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| Affiliations |
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Funding (1)
| 1 | Russian Science Foundation | 17-13-01117 |
Abstract:
The selectivity patterns of iron catalysts of the Fe(PDP) family in aliphatic C–H oxidation with H 2 O 2 have been studied (PDP = N , N ′‐bis(pyridine‐2‐ylmethyl)‐2,2′‐bipyrrolidine). Cyclohexane, adamantane, 1‐bromo‐3,7‐dimethyloctane, 3,7‐dimethyloctyl acetate, (–)‐acetoxy‐ p ‐menthane, and cis ‐1,2‐dimethylcyclohexane were used as substrates. The studied catalyst systems generate low‐spin ( S = 1/2) oxoiron(V) intermediates or high‐spin ( S = 3/2) oxoiron(V) intermediates, depending on the electron‐donating ability of remote substituents at the pyridine rings. The low‐spin perferryl intermediates demonstrate lower stability and higher reactivity toward aliphatic C–H groups of cyclohexane than their high‐spin congeners, according to the measured self‐decay and second‐order rate constants k 1 and k 2 . Unexpectedly, there appears to be no uniform correlation between the spin state of the oxoiron(V) intermediates, and the chemo‐ and regioselectivity of the corresponding catalyst systems in the oxidation of the considered substrates. This contrasts with the asymmetric epoxidations by the same catalyst systems, in which case the epoxidation enantioselectivity increases when passing from the systems featuring the more reactive low‐spin perferryl intermediates to those with their less reactive high‐spin congeners.
Cite:
Zima A.M.
, Lyakin O.Y.
, Bryliakov K.P.
, Talsi E.P.
Low‐Spin and High‐Spin Perferryl Intermediates in Non‐Heme Iron Catalyzed Oxidations of Aliphatic C–H Groups
Chemistry - A European Journal. 2021. V.27. N28. P.7781-7788. DOI: 10.1002/chem.202004395 WOS Scopus РИНЦ ANCAN PMID OpenAlex
Low‐Spin and High‐Spin Perferryl Intermediates in Non‐Heme Iron Catalyzed Oxidations of Aliphatic C–H Groups
Chemistry - A European Journal. 2021. V.27. N28. P.7781-7788. DOI: 10.1002/chem.202004395 WOS Scopus РИНЦ ANCAN PMID OpenAlex
Dates:
| Submitted: | Sep 29, 2020 |
| Accepted: | Mar 29, 2021 |
| Published online: | Mar 29, 2021 |
| Published print: | May 17, 2021 |
Identifiers:
| Web of science: | WOS:000645494000001 |
| Scopus: | 2-s2.0-85105170010 |
| Elibrary: | 46035648 |
| Chemical Abstracts: | 2021:1009054 |
| Chemical Abstracts (print): | 177:60156 |
| PMID: | 33780054 |
| OpenAlex: | W3148336394 |