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. 2023 Aug 16;145(32):17564-17569.
doi: 10.1021/jacs.3c07018. Epub 2023 Aug 2.

C(sp2)-H Hydroxylation via Catalytic 1,4-Ni Migration with N2O

Huihui Zhang  1   2 , Jesus Rodrigalvarez  1 , Ruben Martin  1   3
Affiliations

C(sp2)-H Hydroxylation via Catalytic 1,4-Ni Migration with N2O

Huihui Zhang et al. J Am Chem Soc. .

Abstract

Herein, we report a Ni-catalyzed C(sp2)-H hydroxylation of aryl bromides with N2O as an oxygen-atom donor. The reaction is enabled by a 1,4-Ni translocation that results in ipso/ortho difunctionalized products. Regioselectivity and stereocontrol are dictated by a judicious choice of the ligand backbone, thus giving access to either carbonyl or phenol derivatives and offering an opportunity to repurpose hazardous substances en route to valuable oxygen-containing building blocks.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Oxygen-Transfer Reactions with N2O and Ni
Scheme 2
Scheme 2. sp2 C–H Hydroxylation with N2O via a 1,4-Ni Shift
Scheme 3
Scheme 3. Preliminary Mechanistic Studies
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