Issue 47, 2022

Lewis acid improved dioxygen activation by a non-heme iron(ii) complex towards tryptophan 2,3-dioxygenase activity for olefin oxygenation

Abstract

Dioxygen activation and catalysis around ambient temperature is a long-standing challenge in chemistry. Inspired by the significant roles of the hydrogen bond network in dioxygen activation and catalysis by redox enzymes, this work presents a Lewis acid improved dioxygen activation by an FeII(BPMEN)(OTf)2 complex towards tryptophan 2,3-dioxygenase (TDO) activity for 3-methylindole and common olefinic CC [double bond, length as m-dash] bond oxygenation and cleavage (enzymatic Brønsted acid vs. chemical Lewis acid). It was found that the presence of a Lewis acid such as Sc3+ could substantially improve olefinic CC [double bond, length as m-dash] bond oxygenation and cleavage activity through FeII(BPMEN)(OTf)2 catalyzed dioxygen activation. Notably, a more negative ρ value in the Hammett plot of para-substituted styrene oxygenations was observed in the presence of a stronger Lewis acid, disclosing the enhanced electrophilic oxygenation capability of the putative iron(III) superoxo species through its electrostatic interaction with a stronger Lewis acid. Thereof, this work has demonstrated a new strategy in catalyst design for dioxygen activation and catalysis for olefin oxygenation, a significant process in the chemical industry.

Graphical abstract: Lewis acid improved dioxygen activation by a non-heme iron(ii) complex towards tryptophan 2,3-dioxygenase activity for olefin oxygenation

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
25 Aug 2022
Accepted
07 Nov 2022
First published
09 Nov 2022

Dalton Trans., 2022,51, 18024-18032

Lewis acid improved dioxygen activation by a non-heme iron(II) complex towards tryptophan 2,3-dioxygenase activity for olefin oxygenation

G. Liao, F. Mei, Z. Chen and G. Yin, Dalton Trans., 2022, 51, 18024 DOI: 10.1039/D2DT02769K

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