Enantioselective Formation of α‑Amino Acid Derivatives via [2,3]-Sigmatropic Rearrangement of N‑Acyl Iminosulfinamides

An aza-variation on [2,3]-sigmatropic rearrangement of allylic sulfimides was developed. In this process, enolization of N-acyl iminosulfinamides was followed by O-silylation to generate O-silyl N-iminosulfinyl N,O-ketene aminal intermediates, which undergo a [2,3]-shift to afford α-sulfenylamino im...

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Bibliographic Details
Published in:Organic letters 2023-06, Vol.25 (22), p.4156-4161
Main Authors: Liu, Teng-Fei, Yao, Yun, Lu, Chong-Dao
Format: Article
Language:English
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Summary:An aza-variation on [2,3]-sigmatropic rearrangement of allylic sulfimides was developed. In this process, enolization of N-acyl iminosulfinamides was followed by O-silylation to generate O-silyl N-iminosulfinyl N,O-ketene aminal intermediates, which undergo a [2,3]-shift to afford α-sulfenylamino imidates that were converted to the corresponding carboxamides after desilylation triggered by acidic aqueous workup. Chirality is transferred from the sulfur stereocenter to the α-carbon, thereby enabling the enantioselective installation of an amino group at the α-position of amides.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.3c01448