Work

Control over S(VI)‐Stereogenic Center: NHC‐Catalyzed Enantioselective Synthesis of N ‐Acyl Cyclic Sulfonimidamides

Year: 2025

Type: article

Abstract: The catalytic enantioselective synthesis of aza-sulfur(VI) compounds holds significant potential in pharmaceuticals owing to their broad spectrum of biological properties. Herein, we report the first N-heterocyclic carbene (NHC)-catalyzed enantioselective synthesis of cyclic sulfonimidamides (SIAs). The free N-H containing SIAs often exhibit configurational lability through tautomerization. We investigated this by demonstrating their nonsymmetric nature in both solid state and solution. The in situ generated chiral acylazolium intermediates from easily accessible aldehydes in the presence of NHC and oxidant were trapped with the prochiral cyclic SIA anions, allowing the enantioselective synthesis of configurationally stable N-acyl cyclic SIAs. Mechanistic studies reveal that the present strategy proceeds via the desymmetrization of the prochiral SIA anions. Moreover, the derivatization of the synthesized N-acyl SIAs highlights the practical utility of the present methodology.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.202506929

Authors: Soumen Barik, Fathima Dinsha Paravakkal, Priyanshu Gupta, Palash Roy, Akkattu T. Biju

Institution: Indian Institute of Science Bangalore

Language: English

Topic: N-Heterocyclic Carbenes in Organic and Inorganic Chemistry

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: bronze

Funders: Department of Science and Technology, Ministry of Science and Technology, India, Ministry of Education, India

Award: G4393360203