Iron-Catalyzed Enantioselective Epoxidations with Various Oxidants: Evidence for Different Active Species and Epoxidation Mechanisms Full article
| Journal |
ACS Catalysis
ISSN: 2155-5435 |
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| Output data | Year: 2017, Volume: 7, Number: 1, Pages: 60-69 Pages count : 10 DOI: 10.1021/acscatal.6b02851 | ||||
| Tags | asymmetric epoxidation, bioinspired catalysis, enantioselectivity, EPR, iron, mechanism | ||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Russian Foundation for Basic Research | 16-29-10666 |
| 2 | Federal Agency for Scientific Organizations | V.44.2.4. |
Abstract:
Iron complexes with chiral bipyrrolidine-derived aminopyridine (PDP) ligands are among the most efficient Fe-based bioinspired catalysts for regio- and stereoselective oxidation of C–H and C═C moieties with hydrogen peroxide. Besides hydrogen peroxide, other oxidants (peroxycarboxylic acids and organic hydroperoxides) can be effectively used. In this work, we have examined the mechanistic landscape of the Fe(PDP) catalyst family with various oxidants: H2O2, organic hydroperoxides, and peracids. The combined EPR spectroscopic, enantioselectivity, Hammett, Z-stilbene epoxidation stereoselectivity, and 18O-labeling data witness that the same oxoiron complexes [(L)FeV═O(OC(O)R)]2+ are the actual epoxidizing species in both the catalyst systems (L)Fe/H2O2/carboxylic acid and (L)Fe/AlkylOOH/carboxylic acid. On the contrary, in the systems (L)Fe/R2C(O)OOH (R2 = CH3 or 3–Cl-C6H4), in the presence or in the absence of carboxylic acid, the epoxidation is predominantly conducted by the acylperoxo-iron(III) intermediates [(L)FeIII(OOC(O)R2)]2+, in a concerted fashion.
Cite:
Zima A.M.
, Lyakin O.Y.
, Ottenbacher R.V.
, Bryliakov K.P.
, Talsi E.P.
Iron-Catalyzed Enantioselective Epoxidations with Various Oxidants: Evidence for Different Active Species and Epoxidation Mechanisms
ACS Catalysis. 2017.
V.7. N1. P.60-69. DOI: 10.1021/acscatal.6b02851
WOS
Scopus
РИНЦ
OpenAlex
ANCAN
Iron-Catalyzed Enantioselective Epoxidations with Various Oxidants: Evidence for Different Active Species and Epoxidation Mechanisms
ACS Catalysis. 2017.
V.7. N1. P.60-69. DOI: 10.1021/acscatal.6b02851
WOS
Scopus
РИНЦ
OpenAlex
ANCAN
Files:
Full text from publisher
Dates:
| Submitted: | Oct 6, 2016 |
| Accepted: | Nov 3, 2016 |
| Published online: | Dec 3, 2016 |
| Published print: | Jan 6, 2017 |
Identifiers:
| ≡ Web of science: | WOS:000391783200006 |
| ≡ Scopus: | 2-s2.0-85019668398 |
| ≡ Elibrary: | 32051750 |
| ≡ OpenAlex: | W2551091103 |
| ≡ Chemical Abstracts: | 2016:1821853 |
| ≡ Chemical Abstracts (print): | 166:65135 |