Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 46, Pages 24510-24518Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202106356
Keywords
borylation; carboxylic acid activation; decarbonylative cross-coupling; DFT studies; nickel catalysis
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Funding
- National Key Research and Development Program of China [2018YFA0704502]
- National Natural Science Foundation of China [21931011, 22071241, 22071243]
- Key Research Program of Frontier Sciences of the Chinese Academy of Sciences [QYZDJ-SSW-SLH024]
- Strategic Priority Research Program of the Chinese Academy of Science [XDB20000000]
- Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic
- University of Colorado Denver
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The Ni-catalyzed decarbonylative borylation of (hetero)aryl carboxylic acids with B(2)cat(2) has been achieved without additives, covering a broad substrate scope and tolerating diverse functional groups. Experimental and computational studies revealed a detailed mechanism involving a concerted decarbonylation and reductive elimination step.
The Ni-catalyzed decarbonylative borylation of (hetero)aryl carboxylic acids with B(2)cat(2) has been achieved without recourse to any additives. This Ni-catalyzed method exhibits a broad substrate scope covering poorly reactive non-ortho-substituted (hetero)aryl carboxylic acids, and tolerates diverse functional groups including some of the groups active to Ni-0 catalysts. The key to achieve this decarbonylative borylation reaction is the choice of B(2)cat(2) as a coupling partner that not only acts as a borylating reagent, but also chemoselectively activates aryl carboxylic acids towards oxidative addition of their C(acyl)-O bond to Ni-0 catalyst via the formation of acyloxyboron compounds. A combination of experimental and computational studies reveals a detailed plausible mechanism for this reaction system, which involves a hitherto unknown concerted decarbonylation and reductive elimination step that generates the aryl boronic ester product. This mode of boron-promoted carboxylic acid activation is also applicable to other types of reactions.
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