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- Title
Photocatalytic Asymmetric Acyl Radical Truce–Smiles Rearrangement for the Synthesis of Enantioenriched α‐Aryl Amides.
- Authors
Ma, Wei‐Yang; Leone, Matteo; Derat, Etienne; Retailleau, Pascal; Reddy, Chada Raji; Neuville, Luc; Masson, Géraldine
- Abstract
The radical Truce–Smiles rearrangement is a straightforward strategy for incorporating aryl groups into organic molecules for which asymmetric processes remains rare. By employing a readily available and non‐expensive chiral auxiliary, we developed a highly efficient asymmetric photocatalytic acyl and alkyl radical Truce–Smiles rearrangement of α‐substituted acrylamides using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom–transfer photocatalyst, along with aldehydes or C−H containing precursors. The rearranged products exhibited excellent diastereoselectivities (7 : 1 to >98 : 2 d.r.) and chiral auxiliary was easily removed. Mechanistic studies allowed understanding the transformation in which density functional theory (DFT) calculations provided insights into the stereochemistry‐determining step.
- Subjects
ABSTRACTION reactions; DENSITY functional theory; ARYL group; RADICALS (Chemistry); PHOTOCATALYSIS; ASYMMETRIC synthesis; ALKYL radicals
- Publication
Angewandte Chemie, 2024, Vol 136, Issue 37, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202408154