Determining the Inherent Selectivity for Carbon Radical Hydroxylation Versus Halogenation with Fe(OH)(X) Complexes: Relevance to the Rebound Step in Non-heme Iron Halogenases

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2020 Apr 14

PMID 32281794

Citations 19

Authors

Vishal Yadav

Rodolfo J Rodriguez

Maxime A Siegler

David P Goldberg

Affiliations

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Abstract

The first structural models of the proposed -Fe(OH)(halide) intermediate in the non-heme iron halogenases were synthesized and examined for their inherent reactivity with tertiary carbon radicals. Selective hydroxylation occurs for these -Fe(OH)(X) (X = Cl, Br) complexes in a radical rebound-like process. In contrast, a -Fe(Cl) complex reacts with carbon radicals to give halogenation. These results are discussed in terms of the inherent reactivity of the analogous rebound intermediate in both enzymes and related catalysts.

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