Journal
ORGANIC PROCESS RESEARCH & DEVELOPMENT
Volume 25, Issue 4, Pages 916-925Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.oprd.0c00548
Keywords
Suzuki-Miyaura reaction; aryl chlorides; homogeneous versus heterogeneous; differential selectivity; palladium
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Funding
- Russian Science Foundation [19-13-00051]
- Russian Science Foundation [19-13-00051] Funding Source: Russian Science Foundation
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This study distinguishes between the homogeneous and heterogeneous catalytic mechanisms of Pd catalytic systems in the Suzuki-Miyaura reaction, providing convincing evidence for reactions proceeding simultaneously through both mechanisms. The use of ligand-free conditions suggests that the reaction proceeds in the solution phase through a homogeneous mechanism even when heterogeneous precursors are used, based on differential selectivity under competition conditions.
A distinction between the homogeneous and heterogeneous catalytic mechanisms of a myriad of Pd catalytic systems for the Suzuki-Miyaura reaction has been made based on soluble metal complexes or heterogenized Pd compounds. To date, hypotheses that concern whether the reaction proceeds in the solution phase or on the surface of solid particles, including nanosized ones, have been based on experimental results obtained under different reaction conditions. Moreover, convincing evidence was obtained for reactions proceeding simultaneously through homogeneous and heterogeneous catalytic mechanisms. However, most of the experimental evidence was obtained for relatively reactive aryl bromides and aryl iodides, while insufficient data exists for nonreactive aryl chlorides to make any well-grounded conclusions regarding the homogeneous or heterogeneous nature of the active species. Here, we report the use of ligand-free conditions, which excludes the need to add strong organic ligands, such as phosphines, amines, and carbenes, for the activation of aryl chlorides in the Suzuki-Miyaura reaction. The results suggest that the reaction proceeds in the solution phase through a homogeneous mechanism even when heterogeneous precursors are used. The main reason for this conclusion is the independence of the reaction differential selectivity under the competition of two aryl chlorides or two arylboronic acids, which is based on numerous parameters that only influence the nature of the possible heterogeneous Pd forms when the homogeneous mechanism is realized.
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