期刊
ACS CATALYSIS
卷 11, 期 15, 页码 9578-9587出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c01631
关键词
mechanism; kinetics; density functional theory; gold; decarboxylation; cross-coupling
资金
- University of Minnesota
- National Science Foundation (NSF) [CHE1942223, CHE190050, CHE170089, ACI-1548562]
This study investigates the mechanistic details of a gold-catalyzed decarboxylative cross-coupling, suggesting a high-valent Au(I/III) pathway with a turnover-limiting oxidative addition. The dominant pathway likely involves a silver-mediated decarboxylation followed by an Ag(I) to Au(III) transmetalation. These findings provide insight into the significant counterion effects observed between SbF6- and NTf2-.
While many gold-catalyzed reactions have been thoroughly developed, most are not thought to involve redox events at gold. In contrast, recent advances have demonstrated the feasibility of redox gold catalysis. This report describes a detailed mechanistic investigation of the gold-catalyzed decarboxylative cross-coupling, which likely proceeds via a high-valent Au(I/III) pathway. This investigation includes a kinetic analysis, stoichiometric experiments with Au(III) complexes, and density functional theory calculations. These data support a turnover-limiting oxidative addition to form a Au(III) aryl complex, with an off-cycle resting state. The dominant pathway appears to proceed through a silver-mediated decarboxylation with a subsequent Ag(I) to Au(III) transmetalation. These data provide some rationale for the significant counterion effects between SbF6- and NTf2-.
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