Abstract
A catalytic system for the Heck reaction of fluorinated haloaryls, which involves the first catalytic insertion into a metal-perfluoroaryl bond, has been developed. Pentafluorophenyl complexes of palladium which lack ligands other than halides are used as catalysts. The absence of other ligands besides solvent, halides, and substrates is required for an efficient functionalization. Pentafluoro- and tetrafluoro-substituted haloaryls can be efficiently reacted with terminal and disubstituted olefins, such as styrene, α-methylstyrene, and acrylate esters, but nonactivated alkenes give only moderate yields. Coordination-insertion is rate determining for pentafluoroaryl and tetrafluoroaryl bromides, which can be switched to oxidative addition if a large excess of olefin is used. Thus, the best reaction conditions can be reached by adjusting the actual ratio of haloaryl to olefin for each combination of substrates.
| Original language | English |
|---|---|
| Pages (from-to) | 3679-3684 |
| Number of pages | 6 |
| Journal | Organometallics |
| Volume | 24 |
| Issue number | 15 |
| DOIs | |
| Publication status | Published - Jul 18 2005 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
Catalytic system for the Heck reaction of fluorinated haloaryls. / Albéniz, Ana C.; Espinet, Pablo; Martín-Ruiz, Blanca; Milstein, David.
In: Organometallics, Vol. 24, No. 15, 18.07.2005, p. 3679-3684.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Catalytic system for the Heck reaction of fluorinated haloaryls
AU - Albéniz, Ana C.
AU - Espinet, Pablo
AU - Martín-Ruiz, Blanca
AU - Milstein, David
PY - 2005/7/18
Y1 - 2005/7/18
N2 - A catalytic system for the Heck reaction of fluorinated haloaryls, which involves the first catalytic insertion into a metal-perfluoroaryl bond, has been developed. Pentafluorophenyl complexes of palladium which lack ligands other than halides are used as catalysts. The absence of other ligands besides solvent, halides, and substrates is required for an efficient functionalization. Pentafluoro- and tetrafluoro-substituted haloaryls can be efficiently reacted with terminal and disubstituted olefins, such as styrene, α-methylstyrene, and acrylate esters, but nonactivated alkenes give only moderate yields. Coordination-insertion is rate determining for pentafluoroaryl and tetrafluoroaryl bromides, which can be switched to oxidative addition if a large excess of olefin is used. Thus, the best reaction conditions can be reached by adjusting the actual ratio of haloaryl to olefin for each combination of substrates.
AB - A catalytic system for the Heck reaction of fluorinated haloaryls, which involves the first catalytic insertion into a metal-perfluoroaryl bond, has been developed. Pentafluorophenyl complexes of palladium which lack ligands other than halides are used as catalysts. The absence of other ligands besides solvent, halides, and substrates is required for an efficient functionalization. Pentafluoro- and tetrafluoro-substituted haloaryls can be efficiently reacted with terminal and disubstituted olefins, such as styrene, α-methylstyrene, and acrylate esters, but nonactivated alkenes give only moderate yields. Coordination-insertion is rate determining for pentafluoroaryl and tetrafluoroaryl bromides, which can be switched to oxidative addition if a large excess of olefin is used. Thus, the best reaction conditions can be reached by adjusting the actual ratio of haloaryl to olefin for each combination of substrates.
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U2 - 10.1021/om050017w
DO - 10.1021/om050017w
M3 - Article
VL - 24
SP - 3679
EP - 3684
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 15
ER -