139070-70-5Relevant articles and documents
Chemoselective Alkene Hydrosilylation Catalyzed by Nickel Pincer Complexes
Buslov, Ivan,Becouse, Jeanne,Mazza, Simona,Montandon-Clerc, Mickael,Hu, Xile
, p. 14523 - 14526 (2015)
Chemoselective hydrosilylation of functionalized alkenes is difficult to achieve using base-metal catalysts. Reported herein is that well-defined bis(amino)amide nickel pincer complexes are efficient catalysts for anti-Markovnikov hydrosilylation of terminal alkenes with turnover frequencies of up to 83 000 per hour and turnover numbers of up to 10 000. Alkenes containing amino, ester, amido, ketone, and formyl groups are selectively hydrosilylated. A slight modification of reaction conditions allows tandem isomerization/hydrosilylation reactions of internal alkenes using these nickel catalysts.
Cationic nickel(II)-catalyzed hydrosilylation of alkenes: Role of p, n?type ligand scaffold on selectivity and reactivity
Hossain, Istiak,Schmidt, Joseph A.R.
supporting information, p. 3441 - 3451 (2020/10/09)
Seven structurally similar cationic nickel(II)?alkyl complexes were synthesized by using a series of P, N ligands, and their reactivity was explored in the hydrosilylation of alkenes. More electron-rich phosphines enhanced the overall reactivity of the transformation; in contrast, groups on the imine donor had little impact. Overall, these catalysts displayed reactivity and selectivity that was previously unknown or very rare in nickel-catalyzed hydrosilylation. In reactions with Ph2SiH2, 1,2-disubstituted vinylarenes showed complete benzylic selectivity for silane addition, whereas terminal selectivity was observed for 1,1-disubstituted alkenes. The related PhSiH3 led to exclusively Markovnikov selectivity for monosubstituted vinylarenes with no competing double addition observed. Mechanistic investigations supported the hypothesis that a Ni?H functions as the active species in this catalytic hydrosilylation, which in turn also showed catalytic competence for the silane redistribution reaction, especially with sterically unhindered silanes.
Anti-Markovnikov terminal and gem-olefin hydrosilylation using a κ4-diimine nickel catalyst: selectivity for alkene hydrosilylation over ether C-O bond cleavage
Rock, Christopher L.,Trovitch, Ryan J.
supporting information, p. 461 - 467 (2019/01/09)
The phosphine-substituted α-diimine Ni precursor, (Ph2PPrDI)Ni, has been found to catalyze alkene hydrosilylation in the presence of Ph2SiH2 with turnover frequencies of up to 124 h?1 at 25 °C (990 h?1 at 60 °C). Moreover, the selective hydrosilylation of allylic and vinylic ethers has been demonstrated, even though (Ph2PPrDI)Ni is known to catalyze allyl ester C-O bond hydrosilylation. At 70 °C, this catalyst has been found to mediate the hydrosilylation of ten different gem-olefins, with turnover numbers of up to 740 under neat conditions. Prior and current mechanistic observations suggest that alkene hydrosilylation takes place though a Chalk-Harrod mechanism following phosphine donor dissociation.
Alkene hydrosilylation catalyzed by easily assembled Ni(ii)-carboxylate MOFs
Zhang, Zhikun,Bai, Lichen,Hu, Xile
, p. 3791 - 3795 (2019/04/01)
We report the first Ni MOF catalysts for anti-Markovnikov hydrosilylation of alkenes. These catalysts are bench-stable and easily-assembled from simple Ni salts and carboxylic acids. The best catalyst gives turnover numbers up to 9500 and is robust even a
Non-Precious-Metal Catalytic Systems Involving Iron or Cobalt Carboxylates and Alkyl Isocyanides for Hydrosilylation of Alkenes with Hydrosiloxanes
Noda, Daisuke,Tahara, Atsushi,Sunada, Yusuke,Nagashima, Hideo
supporting information, p. 2480 - 2483 (2016/03/12)
A mixture of an iron or a cobalt carboxylate and an isocyanide ligand catalyzed the hydrosilylation of alkenes with hydrosiloxanes with high efficiency (TON >103) and high selectivity. The Fe catalyst showed excellent activity for hydrosilylation of styrene derivatives, whereas the Co catalyst was widely effective in reaction of alkenes. Both of them catalyzed the reaction with allylic ethers. Chemical modification and cross-linking of silicones were achieved by choosing the right catalyst and reaction conditions.
General and practical one-pot synthesis of dihydrobenzosiloles from styrenes
Kuznetsov, Alexey,Gevorgyan, Vladimir
supporting information; experimental part, p. 914 - 917 (2012/05/05)
A one-pot synthesis of dihydrobenzosiloles from styrenes has been developed. The reaction involves the nickel-catalyzed hydrosilylation of styrene with diphenylsilane, followed by the iridium-catalyzed dehydrogenative cyclization. This method is efficient for both electron-rich and -deficient styrenes and exhibits good functional group tolerance, as well as excellent regioselectivity. The forming dihydrobenzosiloles can be efficiently converted into valuable benzosiloles or 2-hydroxyphenethyl alcohols.
Gold nanoparticles and gold(III) complexes as general and selective hydrosilylation catalysts
Corma, Avelino,Gonzalez-Arellano, Camino,Iglesias, Marta,Sanchez, Felix
, p. 7820 - 7822 (2008/09/19)
(Chemical Equation Presented) Worth their weight in gold: Au/CeO 2 nanoparticles are a highly active catalyst for the hydrosilylation of a large variety of unsaturated compounds with high chemo- and regioselectivity. To understand the nature of the catalytic active sites, AuI and AuIII phosphine-free stable organogold complexes and their supported counterparts were prepared and their relative activity towards hydrosilylation was elucidated.
