Interrogating Pd(II) anion metathesis using a bifunctional chemical probe: a transmetalation switch

John J Molloy, Ciaran P. Seath, Matthew J West, Calum McLaughlin, Neal J. Fazakerley, Alan R. Kennedy, David James Nelson, Allan J. B. Watson

Research output: Contribution to journalLetter

16 Citations (Scopus)

Abstract

Ligand metathesis of Pd(II) complexes is mechanistically essential for cross-coupling. We present a study of halide→OH anion metathesis of (Ar)Pd(II) complexes using vinylBPin as a bifunctional chemical probe with Pd(II)-dependent cross-coupling pathways. We identify the variables that profoundly impact this event and allow control to be leveraged. This then allows control of cross-coupling pathways via promotion or inhibition of organoboron transmetalation, leading to either Suzuki-Miyaura or Mizoroki-Heck products. We show how this transmetalation switch can be used to synthetic gain in a cascade cross-coupling/Diels-Alder reaction, delivering borylated or non-borylated carbocycles, including steroid-like scaffolds.
LanguageEnglish
JournalJournal of the American Chemical Society
Early online date19 Dec 2017
DOIs
Publication statusE-pub ahead of print - 19 Dec 2017

Fingerprint

metathesis
cross coupling
Cycloaddition Reaction
Anions
Negative ions
switches
Steroids
Switches
anions
Ligands
probes
Scaffolds
Diels-Alder reactions
steroids
promotion
halides
cascades
ligands
products

Cite this

Molloy, John J ; Seath, Ciaran P. ; West, Matthew J ; McLaughlin, Calum ; Fazakerley, Neal J. ; Kennedy, Alan R. ; Nelson, David James ; Watson, Allan J. B. / Interrogating Pd(II) anion metathesis using a bifunctional chemical probe : a transmetalation switch. In: Journal of the American Chemical Society. 2017.
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abstract = "Ligand metathesis of Pd(II) complexes is mechanistically essential for cross-coupling. We present a study of halide→OH anion metathesis of (Ar)Pd(II) complexes using vinylBPin as a bifunctional chemical probe with Pd(II)-dependent cross-coupling pathways. We identify the variables that profoundly impact this event and allow control to be leveraged. This then allows control of cross-coupling pathways via promotion or inhibition of organoboron transmetalation, leading to either Suzuki-Miyaura or Mizoroki-Heck products. We show how this transmetalation switch can be used to synthetic gain in a cascade cross-coupling/Diels-Alder reaction, delivering borylated or non-borylated carbocycles, including steroid-like scaffolds.",
author = "Molloy, {John J} and Seath, {Ciaran P.} and West, {Matthew J} and Calum McLaughlin and Fazakerley, {Neal J.} and Kennedy, {Alan R.} and Nelson, {David James} and Watson, {Allan J. B.}",
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Interrogating Pd(II) anion metathesis using a bifunctional chemical probe : a transmetalation switch. / Molloy, John J; Seath, Ciaran P.; West, Matthew J; McLaughlin, Calum; Fazakerley, Neal J.; Kennedy, Alan R.; Nelson, David James; Watson, Allan J. B.

In: Journal of the American Chemical Society, 19.12.2017.

Research output: Contribution to journalLetter

TY - JOUR

T1 - Interrogating Pd(II) anion metathesis using a bifunctional chemical probe

T2 - Journal of the American Chemical Society

AU - Molloy, John J

AU - Seath, Ciaran P.

AU - West, Matthew J

AU - McLaughlin, Calum

AU - Fazakerley, Neal J.

AU - Kennedy, Alan R.

AU - Nelson, David James

AU - Watson, Allan J. B.

N1 - This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Journal of the American Chemical Society, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/jacs.7b11180

PY - 2017/12/19

Y1 - 2017/12/19

N2 - Ligand metathesis of Pd(II) complexes is mechanistically essential for cross-coupling. We present a study of halide→OH anion metathesis of (Ar)Pd(II) complexes using vinylBPin as a bifunctional chemical probe with Pd(II)-dependent cross-coupling pathways. We identify the variables that profoundly impact this event and allow control to be leveraged. This then allows control of cross-coupling pathways via promotion or inhibition of organoboron transmetalation, leading to either Suzuki-Miyaura or Mizoroki-Heck products. We show how this transmetalation switch can be used to synthetic gain in a cascade cross-coupling/Diels-Alder reaction, delivering borylated or non-borylated carbocycles, including steroid-like scaffolds.

AB - Ligand metathesis of Pd(II) complexes is mechanistically essential for cross-coupling. We present a study of halide→OH anion metathesis of (Ar)Pd(II) complexes using vinylBPin as a bifunctional chemical probe with Pd(II)-dependent cross-coupling pathways. We identify the variables that profoundly impact this event and allow control to be leveraged. This then allows control of cross-coupling pathways via promotion or inhibition of organoboron transmetalation, leading to either Suzuki-Miyaura or Mizoroki-Heck products. We show how this transmetalation switch can be used to synthetic gain in a cascade cross-coupling/Diels-Alder reaction, delivering borylated or non-borylated carbocycles, including steroid-like scaffolds.

U2 - 10.1021/jacs.7b11180

DO - 10.1021/jacs.7b11180

M3 - Letter

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

ER -