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

Andy A. Thomas, Scott E. Denmark

Research output: Contribution to journalArticle

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.

Original languageEnglish (US)
Pages (from-to)329-332
Number of pages4
JournalScience
Volume352
Issue number6283
DOIs
StatePublished - Apr 15 2016

Fingerprint

Palladium
Boron
Bearings (structural)
Carbon
Boronic Acids
Stoichiometry
Nuclear magnetic resonance spectroscopy
Oxygen
Catalysts
Kinetics
Temperature

ASJC Scopus subject areas

  • General

Cite this

Pre-transmetalation intermediates in the Suzuki-Miyaura reaction revealed : The missing link. / Thomas, Andy A.; Denmark, Scott E.

In: Science, Vol. 352, No. 6283, 15.04.2016, p. 329-332.

Research output: Contribution to journalArticle

@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.}",
year = "2016",
month = "4",
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",

}

TY - JOUR

T1 - Pre-transmetalation intermediates in the Suzuki-Miyaura reaction revealed

T2 - The missing link

AU - Thomas, Andy A.

AU - Denmark, Scott E.

PY - 2016/4/15

Y1 - 2016/4/15

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84963522319&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84963522319&partnerID=8YFLogxK

U2 - 10.1126/science.aad6981

DO - 10.1126/science.aad6981

M3 - Article

AN - SCOPUS:84963522319

VL - 352

SP - 329

EP - 332

JO - Science

JF - Science

SN - 0036-8075

IS - 6283

ER -