Asymmetric, visible light-mediated radical sulfinyl-Smiles rearrangement to access all-carbon quaternary stereocentres
| Autor: | Marco Müller, Mariia S. Kirillova, Cédric Hervieu, Estíbaliz Merino, Tatiana Suárez, Cristina Nevado |
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| Rok vydání: | 2021 |
| Předmět: |
Chiral auxiliary
010405 organic chemistry Chemistry General Chemical Engineering Radical Aryl Absolute configuration Stereoisomerism General Chemistry 010402 general chemistry 01 natural sciences Combinatorial chemistry 0104 chemical sciences chemistry.chemical_compound Amide Moiety Smiles rearrangement |
| Zdroj: | Nature Chemistry. 13:327-334 |
| ISSN: | 1755-4349 1755-4330 |
| DOI: | 10.1038/s41557-021-00668-4 |
| Popis: | The asymmetric construction of all-carbon quaternary centres within acyclic settings represents a long-standing challenge for synthetic chemists. Alongside polar and radical methods, rearrangement reactions represent an attractive platform, but still broadly applicable methods are in high demand. Here we report an asymmetric, radical sulfinyl-Smiles rearrangement to access acyclic amides that bear an α-all-carbon quaternary centre. Our strategy uses enantioenriched N-arylsulfinyl acrylamides as acceptors for a variety of radicals produced in situ under mild photoredox conditions. The sulfinamido group not only directs the 1,4-migration of the aryl moiety onto the α-carbon of the amide, which thus governs its absolute configuration, but also functions as a traceless chiral auxiliary. The amides obtained in this multicomponent process are prevalent in pharmaceuticals, agrochemicals and bioactive natural products, and can be transformed into valuable chiral α,α-disubstituted acids, oxindoles as well as into β,β-disubstituted amines, highlighting the synthetic potential of this transformation. |
| Databáze: | OpenAIRE |
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