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. 2023 May 1;14(21):5705-5711.
doi: 10.1039/d3sc00874f. eCollection 2023 May 31.

Copper-catalyzed [1,3]-nitrogen rearrangement of O- aryl ketoximes via oxidative addition of N-O bond in inverse electron flow

Mao Suzuki  1 , Masahiro Terada  1 , Itaru Nakamura  2   1
Affiliations

Copper-catalyzed [1,3]-nitrogen rearrangement of O- aryl ketoximes via oxidative addition of N-O bond in inverse electron flow

Mao Suzuki et al. Chem Sci. .

Abstract

The [1,3]-nitrogen rearrangement reactions of O-aryl ketoximes were promoted by N-heterocyclic carbene (NHC)-copper catalysts and BF3·OEt2 as an additive, affording ortho-aminophenol derivatives in good yields. The reaction of substrates with electron-withdrawing substituents on the phenol moiety are accelerated by adding silver salt and modifying the substituent at the nitrogen atom. Density functional theory calculations suggest that the rate-determining step of this reaction is the oxidative addition of the N-O bond of the substrate to the copper catalyst. The negative ρ values of the substituent at both the oxime carbon and phenoxy group indicate that the donation of electrons by the oxygen and nitrogen atoms accelerates the oxidative addition.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. [1,3]-Nitrogen rearrangement reactions of O-arylhydroxylamines.
Scheme 2
Scheme 2. Copper-catalyzed reactions of 1.a a The reaction of 1 (0.1 mmol) was carried out in the presence of IPrCuBr (0.01 mmol) and BF3·OEt2 (0.1 mmol) in 1,2-DCE (0.7 mL) at 50 °C for 1–2 h and the reaction workup was performed by adding saturated ammonium chloride solution. b At 60 °C. c 0.05 mmol scale. d At 80 °C. e 40% of 1hb was recovered. f The reaction was carried out with 10 mol% of AgSbF6. g Yield based on recovered starting material (brsm); 27% of 1kb was recovered. h 84% of 1lb was recovered. i At 70 °C. j 0.5 h.
Scheme 3
Scheme 3. Mechanistic studies.
Fig. 1
Fig. 1. Hammett plot analysis.
Fig. 2
Fig. 2. DFT calculations.
Scheme 4
Scheme 4. Proposed mechanism.
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