Gold‐Catalyzed Cyclization of Yndiamides with Isoxazoles via α‐Imino Gold Fischer Carbenes

Abstract: Gold catalysis is an important method for alkyne functionalization. Here we report the gold‐catalyzed formal [3+2] aminative cyclization of yndiamides and isoxazoles in a direct synthesis of polysubstituted diaminopyrroles, which are important motifs in drug discovery. Key to this process is the formation, and subsequent cyclization, of an α‐imino gold Fischer carbene, which represents a new type of gold carbene intermediate. The reaction proceeds rapidly under mild conditions, with high regioselectivity being achieved by introducing a subtle steric bias between the nitrogen substituents on the yndiamide. DFT calculations revealed that the key to this regioselectivity was the interconversion of isomeric gold keteniminiun ions via a low‐barrier π‐complex transition state, which establishes a Curtin‐Hammett scenario for isoxazole addition. By using benzisoxazoles as substrates, the reaction outcome could be switched to a formal [5+2] cyclization, leading to 1,4‐oxazepines.

Object Details

• Location: Deutsche Nationalbibliothek Frankfurt am Main
• Extent: Online-Ressource
• Language: Englisch

References and Relationships

• Bibliographic citation: Gold‐Catalyzed Cyclization of Yndiamides with Isoxazoles via α‐Imino Gold Fischer Carbenes ; day:25 ; month:10 ; year:2023 ; extent:8 ; Chemistry - a European journal ; (25.10.2023) (gesamt 8)

Contributors, Places and Time

• Creator: Tong, Zixuan ; Smith, Philip J. ; Pickford, Helena D. ; Christensen, Kirsten E. ; Anderson, Edward A.

Further information

• DOI: 10.1002/chem.202302821
• URN: urn:nbn:de:101:1-2023102515492703080322
• Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
• Last update: 14.08.2025, 10:47 AM CEST