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 |
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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 | |
Publication status | Published - 10 Jan 2018 |
Keywords
- cross-coupling
- control
- transmetalation switch