Abstract
| Original language | English |
|---|---|
| Journal | Journal of the American Chemical Society |
| Early online date | 19 Dec 2017 |
| DOIs | |
| Publication status | E-pub ahead of print - 19 Dec 2017 |
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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 journal › Letter
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 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 -