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

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 James Nelson, Allan J. B. Watson

School of Chemistry

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

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^IIcomplexes 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	19 Dec 2017
DOIs	https://doi.org/10.1021/jacs.7b11180
Publication status	Published - 10 Jan 2018

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10.1021/jacs.7b11180

https://strathprints.strath.ac.uk/id/eprint/62678

Allan John Bell Watson
- aw260st-andrews.acuk
- School of Chemistry - Professor of Homogeneous Catalysis
- Sir James Mackenzie Institute for Early Diagnosis
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)PdII 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.}",

note = "J.J.M. thanks GlaxoSmithKline for a Ph.D. studentship. C.P.S. thanks the Carnegie Trust for the Universities of Scotland for a Ph.D. studentship.",

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doi = "10.1021/jacs.7b11180",

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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 James

AU - Watson, Allan J. B.

N1 - J.J.M. thanks GlaxoSmithKline for a Ph.D. studentship. C.P.S. thanks the Carnegie Trust for the Universities of Scotland for a Ph.D. studentship.

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)PdII 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)PdII 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

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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

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Allan John Bell Watson

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