Truce–Smiles Rearrangements by Strain Release: Harnessing Primary Alkyl Radicals for Metal‐Free Arylation

The ring‐opening of 3‐aminocyclobutanone oximes enables easy generation of primary alkyl radicals, capable of undergoing an unprecedented strain‐release, desulfonylative radical Truce–Smiles rearrangement, providing divergent access to valuable 1,3 diamines and unnatural β‐amino acids. Characterized...

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Bibliographic Details
Published in:Angewandte Chemie 2021-10, Vol.133 (41), p.22393-22397
Main Authors: Whalley, David M., Seayad, Jayasree, Greaney, Michael F.
Format: Article
Language:English
Subjects:
Amino acids
arylation
Chemistry
Diamines
Divergence
Free radicals
Migratory species
Oximes
photoredox
radicals
rearrangements
Transition metals
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Summary:The ring‐opening of 3‐aminocyclobutanone oximes enables easy generation of primary alkyl radicals, capable of undergoing an unprecedented strain‐release, desulfonylative radical Truce–Smiles rearrangement, providing divergent access to valuable 1,3 diamines and unnatural β‐amino acids. Characterized by mild conditions and wide scope of migrating species, this protocol allows the modular assembly of sp3‐aryls under transition metal‐free, room‐temperature conditions. The Truce–Smiles rearrangement has proven to be a powerful tool for the synthesis of new sp3‐aryls via ipso substitution. The reaction has been applied to the strain‐release ring‐opening of 3‐aminocyclobutanone oximes, giving cyanide‐free access to β‐amino nitriles under metal‐free, room temperature conditions. The reaction displays a wide scope of migrating arenes.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202108240