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 J. Nelson; Allan J. B. Watson

doi:10.1021/jacs.7b11180

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 J. Nelson, Allan J. B. Watson

Research output: Contribution to journal › Letter › peer-review

37 Citations (Scopus)

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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.

Original language	English
Pages (from-to)	126-130
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	140
Issue number	1
Early online date	22 Dec 2017
DOIs	https://doi.org/10.1021/jacs.7b11180
Publication status	Published - 10 Jan 2018

Keywords

cross-coupling
control
transmetalation switch

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10.1021/jacs.7b11180

Malloy-etal-JACS-2017-Interrogating-Pd-II-anion-metathesis-using-a-bifunctional-chemical-probeAccepted author manuscript, 480 KB

David Nelson, MChem PhD PGDip FRSC FHEA
- david.nelsonstrath.acuk
- Pure And Applied Chemistry - Senior Lecturer
Person: Academic

Cite this

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title = "Interrogating Pd(II) anion metathesis using a bifunctional chemical probe: a transmetalation switch",

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.",

keywords = "cross-coupling, control, transmetalation switch",

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 J.} and Watson, {Allan J. B.}",

note = "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 {\textcopyright} American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/jacs.7b11180",

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day = "10",

doi = "10.1021/jacs.7b11180",

language = "English",

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TY - JOUR

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

T2 - a transmetalation switch

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 J.

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 - 2018/1/10

Y1 - 2018/1/10

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.

KW - cross-coupling

KW - control

KW - transmetalation switch

U2 - 10.1021/jacs.7b11180

DO - 10.1021/jacs.7b11180

M3 - Letter

SN - 0002-7863

VL - 140

SP - 126

EP - 130

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 1

ER -

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

Abstract

Keywords

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David Nelson, MChem PhD PGDip FRSC FHEA

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