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. 2022 Feb 11;24(5):1132-1135.
doi: 10.1021/acs.orglett.1c04122. Epub 2022 Jan 30.

Diarylamine Synthesis via Desulfinylative Smiles Rearrangement

Thomas Sephton  1 , Jonathan M Large  2 , Sam Butterworth  3 , Michael F Greaney  1
Affiliations

Diarylamine Synthesis via Desulfinylative Smiles Rearrangement

Thomas Sephton et al. Org Lett. .

Abstract

Diarylamines are obtained directly from sulfinamides through a novel rearrangement sequence. The transformation is transition metal-free and proceeds under mild conditions, providing facile access to highly sterically hindered diarylamines that are otherwise inaccessible by traditional SNAr chemistry. The reaction highlights the distinct reactivity of the sulfinamide group in Smiles rearrangements versus that of the more common sulfonamides.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Smiles Rearrangements
Scheme 2
Scheme 2. Substrate Scope
Isolated yields, 0.2 mmol scale. 1.0 mmol scale. 0.1 mmol scale.
Scheme 3
Scheme 3. Mechanistic Investigations
Scheme 4
Scheme 4. Proposed Mechanisms
See this image and copyright information in PMC

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