Title

Discovery of Redox-Promoted Brønsted Acid Catalysis in the Gold(III)-Catalyzed Annulation of Phenol and Cyclohexadiene

Publication Name

ACS Catalysis

Abstract

This study discovers a mechanism called redox-promoted Brønsted acid activation using DFT calculations through mechanistic elucidation of the phenol and cyclohexadiene annulation catalyzed by the AuCl3/AgOTf mixed system. According to this mechanism, triflic acid (HOTf) is likely to be the active catalyst generated in situ as a result of the irreversible reduction of gold(III) to gold(I). The corresponding annulation reaction proceeds through two linked catalytic cycles, the first of which conducts the hydroarylation of diene with phenol and is significantly faster than the second, which produces the observed product via intramolecular cyclization. The [OTf]-counteranion of HOTf is found to play an important role in preventing the polymerization of cyclohexadiene. To confirm that HOTf is the active catalyst in both catalytic cycles of the annulation process, we performed experiments with HOTf as the catalyst and achieved the same product as when AuCl3/AgOTf was used as the catalyst. Additionally, NMR spectroscopy and ESI-MS experiments supported the production of the Au(I) ion and HOTf Brønsted acid.

Open Access Status

This publication is not available as open access

Volume

12

Issue

13

First Page

7918

Last Page

7925

Funding Number

DP180100904

Funding Sponsor

Australian Research Council

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Link to publisher version (DOI)

http://dx.doi.org/10.1021/acscatal.2c01194