- Ruthenium-Catalyzed Coupling Reactions of CO2 with C2H4 and Hydrosilanes towards Silyl Esters
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A series of in situ-prepared catalytic systems incorporating RuII precursors and bidentate phosphine ligands has been probed in the reductive carboxylation of ethylene in the presence of triethylsilane as reductant. The catalytic production of propionate and acrylate silyl esters was evidenced by high-throughput screening (HTS) and implemented in batch reactor techniques. The most promising catalyst systems identified were made of Ru(H)(Cl)(CO)(PPh3)3 and 1,4-bis(dicyclohexylphosphino)butane (DCPB) or 1,1’-ferrocene-diyl-bis(cyclohexylphosphine) (DCPF). A marked influence of water on the acrylate/propionate selectivity was noted. Turnover numbers [mol mol(Ru)?1] up to 16 for acrylate and up to 68 for propionate were reached under relatively mild conditions (20 bar, 100 °C, 0.5 mol % Ru, 40 mol % H2O vs. HSiEt3). Possible mechanisms are discussed.
- Kunihiro, Kana,Heyte, Svetlana,Paul, Sébastien,Roisnel, Thierry,Carpentier, Jean-Fran?ois,Kirillov, Evgueni
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supporting information
p. 3997 - 4003
(2021/02/01)
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- Reducing System Trialkylsilane-Transition Metal Acetylacetonate. III. Reduction of Unsaturated Monocarboxylic Acid Chlorides
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Reactions of triethylsilane with acryloyl, methacryloyl, and crotonoyl chlorides in the presence of transition metal (Fe, Co, Ni, Cr, Mn) acetylacetonates yield trialkylchlorosilane and the corresponding unsaturated aldehyde, acid, and triethylsilyl carboxylate. The catalytic activity of the metal acetylacetonates in the reaction of triethylsilane with acryloyl chloride decreases in the order Fe(acac)3 > Co(acac)3 > Ni(acac)2 > Cr(acac)3 >Co(ocac)2 > Mn(acac)3. The reactivity of unsaturated acid chlorides RCOC1 in the reduction decreases in the order R = CH3CH=CH > CH2=C(CH3) > CH2=CH.
- Pukhnarevich,Koval'skaya,Ushakova,Tsykhanskaya,Kopylova,Voronkov
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p. 1257 - 1259
(2007/10/03)
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