Harnessing Noncovalent π‑Type Interactions in Thiourea-Chloride Supramolecular Complexes: Toward the Asymmetric Dearomatization of Diazaheterocycles.

ABSTRACT: Enantioselective dearomatization of diazaheterocycles through anion-binding catalysis has been developed. The process involves the nucleophilic addition of phosphorus nucleophiles to in situ generated N-benzoyliminium chlorides, using a tert-leucine-derived thiourea as an H-bond donor catalyst, thereby providing access to appealing cyclic hydrazino phosphonates and their derivatives. Mechanistic investigations suggest that the low solubility of these salts might favor the formation of a supramolecular thiourea-chloride-iminium 2:1:1 complex, which is proposed as the catalytically relevant species accounting for the observed nonlinear effect. Experimental and computational data support a 4H-activation model via this highly ordered ion pair, in which two thiourea molecules are arranged in an

SUBMITTER: Velazquez M 

PROVIDER: S-EPMC12363210 | biostudies-literature | 2025 Aug

REPOSITORIES: biostudies-literature