Pre-transmetalation intermediates in the Suzuki-Miyaura reaction revealed: The missing link

Despite the widespread application of Suzuki-Miyaura cross-coupling to forge carbon-carbon bonds, the structure of the reactive intermediates underlying the key transmetalation step from the boron reagent to the palladium catalyst remains uncertain. Here we report the use of low-temperature rapid in...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2016-04, Vol.352 (6283), p.329-332
Main Authors: Thomas, Andy A., Denmark, Scott E.
Format: Article
Language:English
Subjects:
Boron
Carbon
Chemical reactions
Magnetic fields
NMR
Nuclear magnetic resonance
Spectroscopy
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Summary:Despite the widespread application of Suzuki-Miyaura cross-coupling to forge carbon-carbon bonds, the structure of the reactive intermediates underlying the key transmetalation step from the boron reagent to the palladium catalyst remains uncertain. Here we report the use of low-temperature rapid injection nuclear magnetic resonance spectroscopy and kinetic studies to generate, observe, and characterize these previously elusive complexes. Specifically, this work establishes the identity of three different species containing palladium-oxygen-boron linkages, a tricoordinate boronic acid complex, and two tetracoordinate boronate complexes with 2:1 and 1:1 stoichiometry with respect to palladium. All of these species transfer their boron-bearing aryl groups to a coordinatively unsaturated palladium center in the critical transmetalation event.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.aad6981