Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 59, Issue 28, Pages 11600-11606Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202003632
Keywords
photochemistry; rearrangement; SNAr; trifluoromethylation; urea
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Funding
- EPSRC Centre for Doctoral Training in Catalysis
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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 alpha-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 alpha,beta-difuctionalisation of a carbon-carbon double bond, and proceeds under mild conditions with visible light and a readily available organic photocatalyst. The products are alpha,alpha-diaryl alkylureas typically functionalized with F or P substituents that may be readily converted into alpha,alpha-diaryl alkylamines.
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