Oxygenolytic cleavage of 1,2-diols with dioxygen by a mononuclear nonheme iron complex: Mimicking the reaction of myo-inositol oxygenase.

Autor: Sutradhar S; School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A&2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India., Rahaman R; School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A&2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India; Department of Chemistry, Krishnagar Government College, Krishnagar, West Bengal 741101, India., Bhattacharya S; School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A&2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India., Paul S; Department of Chemistry, Bangabasi Morning College, 19 Rajkumar Chakraborty Sarani, Kolkata 700009, India., Paine TK; School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A&2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India. Electronic address: ictkp@iacs.res.in.
Jazyk: angličtina
Zdroj: Journal of inorganic biochemistry [J Inorg Biochem] 2024 Aug; Vol. 257, pp. 112611. Date of Electronic Publication: 2024 May 11.
DOI: 10.1016/j.jinorgbio.2024.112611
Abstrakt: A mononuclear iron(II) complex, [(Tp Ph2 )Fe II (OTf)(CH 3 CN)] (1) (Tp Ph2  = hydrotris(3,5-diphenylpyrazol-1-yl)borate, OTf = triflate) has been isolated and its efficiency toward the aliphatic CC bond cleavage reaction of 1,2-diols with dioxygen has been investigated. Separate reactions between 1 and different 1,2-diolates form the corresponding iron(II)-diolate complexes in solution. While the iron(II) complex of the tetradentate TPA (tris(2-pyridylmethyl)amine) ligand is not efficient in affecting the CC cleavage of 1,2-diol with dioxygen, complex 1 displays catalytic activity to afford carboxylic acid and aldehyde. Isotope labeling studies with 18 O 2 reveal that one oxygen atom from dioxygen is incorporated into the carboxylic acid product. The oxygenative CC cleavage reactions occur on the 1,2-diols containing at least one α-H atom. The kinetic isotope effect value of 5.7 supports the abstraction of an α-H by an iron(III)-superoxo species to propagate the CC cleavage reactions. The oxidative cleavage of 1,2-diolates by the iron(II) complex mimics the reaction catalyzed by the nonheme diiron enzyme, myo-inositol oxygenase.
Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2023. Published by Elsevier Inc.)
Databáze: MEDLINE
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