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

Author:

Tong Zixuan1,Smith Philip J.1,Pickford Helena D.1,Christensen Kirsten E.1,Anderson Edward A.1ORCID

Affiliation:

1. Chemistry Research Laboratory Department of Chemistry University of Oxford 12 Mansfield Road Oxford OX1 3TA UK

Abstract

AbstractGold 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.

Funder

Engineering and Physical Sciences Research Council

Publisher

Wiley

Subject

General Chemistry,Catalysis,Organic Chemistry

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