Accessing Perfluoroaryl Sulfonimidamides and Sulfoximines via Photogenerated Perfluoroaryl Nitrenes: Synthesis and Application as a Chiral Auxiliary

Abstract

Sulfonimidamides (SIAs) and sulfoximines (SOIs) have attracted attention due to their potential in agriculture and in medicinal chemistry as bioisosteres of biologically active compounds, and new synthetic methods are needed to access and explore these compounds. Herein, we present a light-promoted generation of perfluorinated aromatic nitrenes, from perfluorinated azides, that subsequently are allowed to react with sulfinamides and sulfoxides, generating achiral and chiral SIAs and SOIs. One of the enantiopure SIAs was evaluated as a novel chiral auxiliary in Grignard additions to the imines yielding the product in up to 96:4 diastereomeric ratio.

Mechanochemical Iron‐Catalyzed Nitrene Transfer Reactions: Direct Synthesis of N‐Acyl Sulfonimidamides from Sulfinamides and Dioxazolones

“…If so, stoichiometric amounts of hypervalent iodine reagents were mostly used as oxidants. An alternative was reported in 2021 by Dinér and co‐workers, who developed a light‐promoted nitrene‐involving strategy for such transformations [14] . Although synthetically appealing, the applicability of this method remained limited due to the use of toxic and explosive azides as nitrene precursors and the requirement of a fluorinated organic solvent and inert reaction conditions.…”

Recent Advances for Chiral Sulfoxides in Asymmetric Catalysis

“…Chiral sulfoxide compounds play an important role in asymmetric synthesis as a variety of auxiliaries, [73] ligands [74] and catalysts. [75] They are also the pharmacodynamic groups of best-selling drugs and can be used in drug design.…”

Ultralight aerogels via supramolecular polymerization of a new chiral perfluoropyridine-based sulfonimidamide organogelator

“…[41][42][43][44][45][46][47][48][49][50][51][52][53] Recently, we developed a synthesis of enantiopure sulfonimidamides via a light-mediated reaction between perfluoroaryl azides (PPFA) and sulfinamides (SA). 54 Serendipitously, we discovered that one of the synthesized compounds, (S)-SIA, exhibited gel-forming properties as revealed by the gelation of the reaction mixture. Due to its ability to gelate nonpolar solvents, we set out to investigate the self-assembly properties of low-molecular weight gelators (LMWG, MW = 285 g mol −1 ) that are based on this novel chiral sulfonimidamide scaffold (S)-SIA.…”