Au–Ag Bimetallic Catalysis: 3‐Alkynyl Benzofurans from Phenols via Tandem C−H Alkynylation/Oxy‐Alkynylation

• Published in: Angewandte Chemie International Edition Vol. 60; no. 19; pp. 10637 - 10642
• Main Authors: Hu, Long, Dietl, Martin C., Han, Chunyu, Rudolph, Matthias, Rominger, Frank, Hashmi, A. Stephen K.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 03.05.2021; Wiley Subscription Services, Inc; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: Acidity; Alkynylation; Au–Ag bimetallic catalysis; Benzofurans; Bimetals; Catalysis; Chemical bonds; Chemistry; Chemistry, Multidisciplinary; Communication; Communications; Functional groups; Gold; Phenols; Physical Sciences; Science & Technology; Silver; Substrates; Alkynylation; Phenols; Ag bimetallic catalysis; Benzofurans; Au– Au-Ag bimetallic catalysis
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202016595

The development of new methodologies enabling a facile access to valuable heterocyclic frameworks still is an important subject of research. In this context, we describe a dual catalytic cycle merging C−H alkynylation of phenols and oxy‐alkynylation of the newly introduced triple bond by using a unique redox property and the carbophilic π acidity of gold. Mechanistic studies support the participation of a bimetallic gold–silver species. The one‐pot protocol offers a direct, simple, and regio‐specific approach to 3‐alkynyl benzofurans from readily available phenols. A broad range of substrates, including heterocycles, is transferred with excellent functional group tolerance. Thus, this methodology can be used for the late‐stage incorporation of benzofurans. A mild and general synthesis of 3‐alkynylbenzofurans from readily available phenols by Au–Ag bimetallic catalysis has been developed. Importantly, this also advances our mechanistic understanding of the “silver effect” in gold redox chemistry.