Abstract
We report here that the undesired hydrodehalogenation in cross-coupling reactions with fluorinated substrates involves water as a possible hydrogen source. Moreover, the product distribution (hydrodehalogenation vs carbon-carbon coupling) can be controlled by varying the phosphine substituents. Significant hydrodehalogenation occurs prior to the formation of Ar F-Pd(II)-Br complexes. DFT calculations were used to evaluate a direct hydrodehalogenation route with a phosphine and water. These findings provide new mechanistic insight into aryl-Br bond activation with fluorinated substrates and selective arene functionalization.
| Original language | English |
|---|---|
| Pages (from-to) | 1271-1274 |
| Number of pages | 4 |
| Journal | Organometallics |
| Volume | 31 |
| Issue number | 4 |
| DOIs | |
| Publication status | Published - Feb 27 2012 |
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ASJC Scopus subject areas
- Organic Chemistry
- Physical and Theoretical Chemistry
- Inorganic Chemistry
Cite this
Palladium-catalyzed cross-coupling reactions with fluorinated substrates : Mechanistic insights into the undesired hydrodehalogenation of aryl halides. / Orbach, Meital; Choudhury, Joyanta; Lahav, Michal; Zenkina, Olena V.; Diskin-Posner, Yael; Leitus, Gregory; Iron, Mark A.; van der Boom, Milko.
In: Organometallics, Vol. 31, No. 4, 27.02.2012, p. 1271-1274.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Palladium-catalyzed cross-coupling reactions with fluorinated substrates
T2 - Mechanistic insights into the undesired hydrodehalogenation of aryl halides
AU - Orbach, Meital
AU - Choudhury, Joyanta
AU - Lahav, Michal
AU - Zenkina, Olena V.
AU - Diskin-Posner, Yael
AU - Leitus, Gregory
AU - Iron, Mark A.
AU - van der Boom, Milko
PY - 2012/2/27
Y1 - 2012/2/27
N2 - We report here that the undesired hydrodehalogenation in cross-coupling reactions with fluorinated substrates involves water as a possible hydrogen source. Moreover, the product distribution (hydrodehalogenation vs carbon-carbon coupling) can be controlled by varying the phosphine substituents. Significant hydrodehalogenation occurs prior to the formation of Ar F-Pd(II)-Br complexes. DFT calculations were used to evaluate a direct hydrodehalogenation route with a phosphine and water. These findings provide new mechanistic insight into aryl-Br bond activation with fluorinated substrates and selective arene functionalization.
AB - We report here that the undesired hydrodehalogenation in cross-coupling reactions with fluorinated substrates involves water as a possible hydrogen source. Moreover, the product distribution (hydrodehalogenation vs carbon-carbon coupling) can be controlled by varying the phosphine substituents. Significant hydrodehalogenation occurs prior to the formation of Ar F-Pd(II)-Br complexes. DFT calculations were used to evaluate a direct hydrodehalogenation route with a phosphine and water. These findings provide new mechanistic insight into aryl-Br bond activation with fluorinated substrates and selective arene functionalization.
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UR - http://www.scopus.com/inward/citedby.url?scp=84857576057&partnerID=8YFLogxK
U2 - 10.1021/om200898t
DO - 10.1021/om200898t
M3 - Article
VL - 31
SP - 1271
EP - 1274
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 4
ER -