Asymmetric Epoxidation vs syn-Hydroxy-Acyloxylation of Olefins in the Presence of Sterically Demanding Nonheme Manganese Complexes Full article
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ACS Catalysis
ISSN: 2155-5435 |
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| Output data | Year: 2024, Volume: 14, Pages: 498-507 Pages count : 10 DOI: 10.1021/acscatal.3c04832 | ||||||
| Tags | asymmetric catalysis; biomimetic chemistry; epoxidation; hydrogen peroxide; manganese; syn-addition | ||||||
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| Affiliations |
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Funding (1)
| 1 | Ministry of Science and Higher Education of the Russian Federation | ГЗ-2021-2023 |
Abstract:
Herewith, we present another facet of the versatile catalytic reactivity of bulky bis-amino-bis-pyridylmethyl Mn complexes: besides highly enantioselective (up to 99% ee) epoxidation, benzhydryl-substituted Mn catalysts have been found to convert olefinic substrates into the products of syn-addition to the C═C bond, hydroxy-carboxylates, that can prevail under certain conditions. The mechanism of syn-hydroxy-acyloxylation is discussed, with the data obtained providing evidence in favor of the so far lacking direct enantioselective OH and OC(O)R transfer from the high-valent Mn active species to the olefinic C═C group. Such a mechanism is conceptually reminiscent of Rieske dioxygenases that catalyze enantioselective 1,2-dihydroxylation of C═C bonds, simultaneously incorporating two cis-ligands from the reactive metal center into the resulting diol in a syn-selective fashion.
Cite:
Sherstyuk V.A.
, Ottenbacher R.V.
, Talsi E.P.
, Bryliakov K.P.
Asymmetric Epoxidation vs syn-Hydroxy-Acyloxylation of Olefins in the Presence of Sterically Demanding Nonheme Manganese Complexes
ACS Catalysis. 2024. V.14. P.498-507. DOI: 10.1021/acscatal.3c04832 WOS Scopus РИНЦ ANCAN OpenAlex
Asymmetric Epoxidation vs syn-Hydroxy-Acyloxylation of Olefins in the Presence of Sterically Demanding Nonheme Manganese Complexes
ACS Catalysis. 2024. V.14. P.498-507. DOI: 10.1021/acscatal.3c04832 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Oct 10, 2023 |
| Accepted: | Dec 12, 2023 |
| Published online: | Dec 22, 2023 |
| Published print: | Jan 5, 2024 |
Identifiers:
| Web of science: | WOS:001137558600001 |
| Scopus: | 2-s2.0-85181805299 |
| Elibrary: | 65520394 |
| Chemical Abstracts: | 2023:2708816 |
| Chemical Abstracts (print): | 185:180692 |
| OpenAlex: | W4390114514 |