High-Spin and Low-Spin State Perferryl Intermediates: Reactivity-Selectivity Correlation in Fe(PDP) Catalyzed Oxidation of (+)-Sclareolide Full article
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ChemCatChem
ISSN: 1867-3880 , E-ISSN: 1867-3899 |
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| Output data | Year: 2022, Volume: 14, Number: 2, Article number : e202101430, Pages count : 5 DOI: 10.1002/cctc.202101430 | ||
| Tags | homogeneous catalysis; Biomimetic chemistry; C-H Activation; Regioselectivity; Reaction mechanisms | ||
| Authors |
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| Affiliations |
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Funding (1)
| 1 | Russian Science Foundation | 17-13-01117 |
Abstract:
Five iron complexes of the Fe(PDP) family, giving rise to the low-spin ( S = 1/2) and high-spin
( S = 3/2) perferryl oxygen-transferring intermediates, have been screened in the C-H oxidation of the bulky steroidal substrate (3a R )-(+)-sclareolide with H2O2 . The regioselectivity of oxidation (preferentially at the C2 methylenic site) increases when passing from the catalyst systems exhibiting more reactive, low-spin perferryl oxygen-transferring species, to those featuring their less reactive, high-spin counterparts. Furthermore, the C2 hydroxylation chemoselectivity increases in the same order, being the highest for the least reactive intermediate in the series; this observation is explained in terms of the more product-like transition state.
Cite:
Zima A.M.
, Babushkin D.E.
, Lyakin O.Y.
, Talsi E.P.
, Bryliakov K.P.
High-Spin and Low-Spin State Perferryl Intermediates: Reactivity-Selectivity Correlation in Fe(PDP) Catalyzed Oxidation of (+)-Sclareolide
ChemCatChem. 2022. V.14. N2. e202101430 :1-5. DOI: 10.1002/cctc.202101430 WOS Scopus РИНЦ AN OpenAlex
High-Spin and Low-Spin State Perferryl Intermediates: Reactivity-Selectivity Correlation in Fe(PDP) Catalyzed Oxidation of (+)-Sclareolide
ChemCatChem. 2022. V.14. N2. e202101430 :1-5. DOI: 10.1002/cctc.202101430 WOS Scopus РИНЦ AN OpenAlex
Dates:
| Submitted: | Sep 22, 2021 |
| Accepted: | Nov 12, 2021 |
| Published online: | Nov 19, 2021 |
| Published print: | Jan 21, 2022 |
Identifiers:
| Web of science: | WOS:000724234200001 |
| Scopus: | 2-s2.0-85120303223 |
| Elibrary: | 47537396 |
| Chemical Abstracts: | 2021:2661477 |
| OpenAlex: | W3215398275 |