785794-78-7Relevant articles and documents
Heterogeneous Catalytic Hydroarylation of Olefins at a Nanoscopic Aluminum Chlorofluoride
Calvo, Beatriz,Wuttke, Jan,Braun, Thomas,Kemnitz, Erhard
, p. 1945 - 1950 (2016)
We report on hydroarylation reactions of arenes with olefins under very mild conditions catalyzed heterogeneously by aluminum chlorofluoride (ACF; AlClxF3?x, x≈0.05–0.25). The reactions of benzene and toluene with ethylene or propylene proceed with high conversions to afford various alkylated arenes. For cyclohexene and 1-hexene, the reactions require higher temperatures and the conversions are lower. ACF also catalyzes the hydroarylation of 1,3,5-trifluorobenzene and pentafluorobenzene with ethylene and propylene. The alkylations of arenes with non-fluorinated olefins resemble typical Friedel–Crafts chemistry to give rise to Markovnikov regioselectivity. The reaction of CF3CH=CH2 with benzene proceeds with anti-Markovnikov regioselectivity to give the fluorinated olefin PhCHCH=CF2 and the alkylation product PhCH2CH2CF3 as products of C?F and C?H activation.
Manganese-Catalyzed Dehydrogenative Silylation of Alkenes following Two Parallel Inner-Sphere Pathways
Weber, Stefan,Glavic, Manuel,St?ger, Berthold,Pittenauer, Ernst,Podewitz, Maren,Veiros, Luis F.,Kirchner, Karl
supporting information, p. 17825 - 17832 (2021/11/04)
We report on an additive-free Mn(I)-catalyzed dehydrogenative silylation of terminal alkenes. The most active precatalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe)(CO)3(CH2CH2CH3)]. The catalytic process is initiated by migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate which undergoes rapid Si-H bond cleavage of the silane HSiR3 forming the active 16e- Mn(I) silyl catalyst [Mn(dippe)(CO)2(SiR3)] together with liberated butanal. A broad variety of aromatic and aliphatic alkenes was efficiently and selectively converted into E-vinylsilanes and allylsilanes, respectively, at room temperature. Mechanistic insights are provided based on experimental data and DFT calculations revealing that two parallel reaction pathways are operative: an acceptorless reaction pathway involving dihydrogen release and a pathway requiring an alkene as sacrificial hydrogen acceptor.
Intermolecular hydroarylation of unactivated olefins catalyzed by homogeneous platinum complexes
Luedtke, Avery T.,Goldberg, Karen I.
supporting information; experimental part, p. 7694 - 7696 (2009/04/11)
Designing catalysts: The five-coordinate platinum(IV) complex A and the platinum(II) trans complex B act as precatalysts for the hydroarylation of unactivated olefins. The catalytic cycle features an aryl-olefin insertion at PtII and a C-H bond activation of the arene solvent as key steps. The Pt II cis complex C has been observed in hydroarylation reactions of ethylene with benzene.