Intermolecular 1,2-Difunctionalization of Nitriles via Redox Gold Catalysis: Synthesis of Benzoxazoles and Benzimidazoles

Chengzhi Xu; Zhenyan Xu; Yifeng Chen; Ming Chen; Yuanhong Liu

doi:10.1002/chem.202404368

Intermolecular 1,2-Difunctionalization of Nitriles via Redox Gold Catalysis: Synthesis of Benzoxazoles and Benzimidazoles

Chemistry. 2025 Jan 8:e202404368. doi: 10.1002/chem.202404368. Online ahead of print.

Authors

Chengzhi Xu¹, Zhenyan Xu², Yifeng Chen², Ming Chen¹, Yuanhong Liu³

Affiliations

¹ Changzhou University, School of Petrochemical Engineering, CHINA.
² East China University of Science and Technology, School of Chemistry and Molecular Engineering, CHINA.
³ Shanghai Institute of Organic Chemistry, State Key Laboratory of Organometallic Chemistry, 354 Fenglin Lu,, 200032, Shanghai, CHINA.

PMID: 39780426
DOI: 10.1002/chem.202404368

Abstract

The unprecedent gold-catalyzed intermolecular 1,2-difunctionalization of nitriles with aryl iodides via Au(I)/Au(III) redox catalysis has been developed, providing an expedient route to the synthesis of benzoxazoles and benzimidazoles with broad substrate scope and high functional compatibility. Mechanistic investigation reveals that the Au(III)-Ar species generated via oxidative addition of o-iodophenol to MeDalphosAu+, serves as a key intermediate. Particularly and this annulation is initiated by oxidative addition, rather than the nucleophilic attack of the phenol moiety in o-iodophenol towards the nitrile. The method was also applied to the synthesis of poly aza-heterocycles via a cascade Au(I)/Au(III) and Au(I) catalysis relay.

Keywords: gold redox catalysis * difunctionalization * nitriles * oxidative addition * heterocycles.