Structural, Kinetic, and Computational Characterization of the Elusive Arylpalladium(II)boronate Complexes in the Suzuki-Miyaura Reaction

Andy A. Thomas, Hao Wang, Andrew F. Zahrt, Scott E. Denmark

Research output: Contribution to journalArticle

Abstract

The existence of the oft-invoked intermediates containing the crucial Pd-O-B subunit, the “missing link”, has been established in the Suzuki-Miyaura cross-coupling reaction. The use of low-temperature, rapid injection NMR spectroscopy (RI-NMR), kinetic studies, and computational analysis has enabled the generation, observation, and characterization of these highly elusive species. The ability to confirm the intermediacy of Pd-O-B-containing species provided the opportunity to clarify mechanistic aspects of the transfer of the organic moiety from boron to palladium in the key transmetalation step. Specifically, these studies establish the identity of two different intermediates containing Pd-O-B linkages, a tri-coordinate (6-B-3) boronic acid complex and a tetra-coordinate (8-B-4) boronate complex, both of which undergo transmetalation leading to the cross-coupling product. Two distinct mechanistic pathways have been elucidated for stoichiometric reactions of these complexes: (1) transmetalation via an unactivated 6-B-3 intermediate that dominates in the presence of an excess of ligand, and (2) transmetalation via an activated 8-B-4 intermediate that takes place with a deficiency of ligand.

Original languageEnglish (US)
Pages (from-to)3805-3821
Number of pages17
JournalJournal of the American Chemical Society
Volume139
Issue number10
DOIs
StatePublished - Mar 15 2017

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ligand
Ligands
Boronic Acids
kinetics
Kinetics
Boron
Cross Reactions
palladium
Palladium
boron
Nuclear magnetic resonance spectroscopy
nuclear magnetic resonance
Magnetic Resonance Spectroscopy
spectroscopy
Observation
Injections
Temperature
Acids
acid
analysis

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Structural, Kinetic, and Computational Characterization of the Elusive Arylpalladium(II)boronate Complexes in the Suzuki-Miyaura Reaction. / Thomas, Andy A.; Wang, Hao; Zahrt, Andrew F.; Denmark, Scott E.

In: Journal of the American Chemical Society, Vol. 139, No. 10, 15.03.2017, p. 3805-3821.

Research output: Contribution to journalArticle

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