Photocatalytic Difunctionalization of Vinyl Ureas by Radical Addition Polar Truce–Smiles Rearrangement Cascades

Research output: Contribution to journalArticle (Academic Journal)peer-review

Abstract

We report tandem alkyl‐arylations and phosphonyl‐arylations of vinyl ureas by way of a photocatalytic radical‐polar crossover mechanism. Addition of photoredox‐generated radicals to the alkene forms a new C−C or C−P bond and generates a product radical adjacent to the urea function. Reductive termination of the photocatalytic cycle generates an anion that undergoes a polar Truce–Smiles rearrangement, forming a C−C bond. The reaction is successful with a range of α‐fluorinated alkyl sodium sulfinate salts and diarylphosphine oxides as radical precursors, and the conformationally accelerated Truce–Smiles rearrangement is not restricted by the electronic nature of the migrating aromatic ring. Formally the reaction constitutes an α,β‐difuctionalisation of a carbon–carbon double bond, and proceeds under mild conditions with visible light and a readily available organic photocatalyst. The products are α,α‐diaryl alkylureas typically functionalized with F or P substituents that may be readily converted into α,α‐diaryl alkylamines.
Original languageEnglish
JournalAngewandte Chemie - International Edition
Early online date30 Mar 2020
DOIs
Publication statusPublished - 8 May 2020

Keywords

  • photochemistry
  • rearrangement
  • SNAr
  • trifluoromethylation
  • urea

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