Aliphatic C-H Azidation by Mn Based Mimics of α-Ketoglutarate Dependent Enzymes Full article
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Journal of Catalysis
ISSN: 0021-9517 , E-ISSN: 1090-2694 |
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| Output data | Year: 2024, Volume: 429, Article number : 115275, Pages count : 6 DOI: 10.1016/j.jcat.2023.115275 | ||||||||
| Tags | Asymmetric catalysis, Azidation, C-H activation, Enzyme models, Hydrogen peroxide, Manganese | ||||||||
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Abstract:
α-Ketoglutarate dependent nonheme halogenases catalyze regioselective functionalization of aliphatic Csingle bondH bonds via H abstraction by the ferryl site of the [X−FeIV=O] intermediate, followed by radical rebound to an adjacent halogen ligand X at the same Fe center. Herein we report biomimetic nonheme Mn complexes, possessing two labile cis-α coordination sites and capable of catalyzing the enantioselective azidation of C(sp3)−H groups. Proper ligand environment of the active sites imposes steric constraints on HO−Mn rebound, thus accounting for preferential C-radical rebound to the adjacent N3−Mn ligand. Such mechanism of selectivity control is analogous to that operating in the prototypical α-ketoglutarate-dependent nonheme iron halogenases.
Cite:
Ottenbacher R.V.
, Lubov D.P.
, Samsonenko D.G.
, Nefedov A.A.
, Bryliakov K.P.
Aliphatic C-H Azidation by Mn Based Mimics of α-Ketoglutarate Dependent Enzymes
Journal of Catalysis. 2024. V.429. 115275 :1-6. DOI: 10.1016/j.jcat.2023.115275 WOS Scopus РИНЦ OpenAlex
Aliphatic C-H Azidation by Mn Based Mimics of α-Ketoglutarate Dependent Enzymes
Journal of Catalysis. 2024. V.429. 115275 :1-6. DOI: 10.1016/j.jcat.2023.115275 WOS Scopus РИНЦ OpenAlex
Dates:
| Submitted: | Nov 21, 2023 |
| Accepted: | Dec 21, 2023 |
| Published online: | Dec 30, 2023 |
| Published print: | Jan 1, 2024 |
Identifiers:
| Web of science: | WOS:001166120900001 |
| Scopus: | 2-s2.0-85181140936 |
| Elibrary: | 65845990 |
| OpenAlex: | W4390277711 |