@article{8ef01f9b79a34efd8c2e862cd27f4bc7,
title = "Pre-transmetalation intermediates in the Suzuki-Miyaura reaction revealed: The missing link",
abstract = "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.",
author = "Thomas, {Andy A.} and Denmark, {Scott E.}",
note = "Funding Information: We are grateful for generous financial support from the NSF (CHE-1012663 and CHE-1151566). A.A.T. is grateful to the University of Illinois for graduate fellowships. We thank L. Zhu for helpful suggestions regarding NMR spectroscopy. Some of the data presented here were collected in the Core Facilities of the Carl R. Woese Institute for Genomic Biology on a 600-MHz NMR instrument (funded by NIH grant S10-RR028833) or at the Integrated Molecular Structure Education and Research Center at Northwestern University. Full experimental procedures, characterization and kinetic data, and copies of the 1H, 13C, 31P, 19F, 11B, NOE, and exchange spectra can be found in the supplementary materials. Publisher Copyright: {\textcopyright} 2016, American Association for the Advancement of Science. All rights reserved.",
year = "2016",
month = apr,
day = "15",
doi = "10.1126/science.aad6981",
language = "English (US)",
volume = "352",
pages = "329--332",
journal = "Science",
issn = "0036-8075",
publisher = "American Association for the Advancement of Science",
number = "6283",
}