Effect of Fluorinated Alcohols on the Reactivity and Selectivity of the Oxoiron(V) Intermediates in C(sp 3 )–H Oxidations | Sciact - CRIS-system of Boreskov Institute of Catalysis

Effect of Fluorinated Alcohols on the Reactivity and Selectivity of the Oxoiron(V) Intermediates in C(sp 3 )–H Oxidations Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2026, DOI: 10.1021/acs.inorgchem.5c05812

Authors

Zima Alexandra M. ¹ , Lyakin Oleg Y. ¹ , Bryliakova Anna A. ² , Bryliakov Konstantin P. ² , Talsi Evgenii P. ¹

Affiliations

1	Boreskov Institute of Catalysis, Novosibirsk 630090, Russia
2	Zelinsky Institute of Organic Chemistry, Moscow 119991, Russia

Funding (2)

1	Ministry of Science and Higher Education of the Russian Federation	FWUR-2024-0032
2	Russian Science Foundation	25-13-00108 (125071708733-8)

In recent years, β-fluorinated alcohols have been increasingly utilized as reaction solvents in a variety of direct hydroxylations of aliphatic C–H bonds, catalyzed by bioinspired Fe-, Mn-, Ni-, and Pd-based catalysts. However, direct experimental data related to the effect of fluorinated alcohols on the reactivity of the key high-valent metal-oxo intermediates have been lacking. Herein, such data are presented, witnessing the promoting effect of 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) on the intrinsic reactivity of the low-spin intermediate [(PDPMe2OMe)FeV=O(OCOCH3)](OTf)2 (1a) toward methylcyclopentane (mcp) and cis-1,2-dimethylcyclohexane (dmch) (PDPX-substituted N,N′-bis(pyridin-2-ylmethyl)-(S,S)-2,2′-bipyrrolidine). This effect is pronounced in the presence of HFIP. In contrast, for the high-spin intermediate [(PDPNMe2)FeV=O(OCOCH3)](OTf)2 (2a), such a promoting effect of fluorinated alcohols was not revealed. The conversion of mcp and dmch in the corresponding systems 1/H2O2/AA and 2/H2O2/AA in HFIP or TFE increases if compared with CH3CN, with the selectivity for tertiary (3°) C–H sites simultaneously decreasing at the expense of more significant engagement of secondary C–H sites into the oxidation. A detailed DFT-based computational study suggests that the reactivity enhancement upon the addition of fluorinated alcohols is due to hydrogen bonding between the fluorinated alcohol and the perferryl active species, which reduces the potential barrier for H abstraction.

Zima A.M. , Lyakin O.Y. , Bryliakova A.A. , Bryliakov K.P. , Talsi E.P.
Effect of Fluorinated Alcohols on the Reactivity and Selectivity of the Oxoiron(V) Intermediates in C(sp 3 )–H Oxidations
Inorganic Chemistry. 2026. DOI: 10.1021/acs.inorgchem.5c05812 OpenAlex

Submitted:	Dec 12, 2025
Accepted:	Jan 14, 2026
Published online:	Jan 22, 2026

OpenAlex:

W7125383047

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