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Ruthenium‐Catalyzed Coupling Reactions of CO 2 with C 2 H 4 and Hydrosilanes towards Silyl Esters

2020; Wiley; Volume: 27; Issue: 12 Linguagem: Inglês

10.1002/chem.202005083

1521-3765

Kana Kunihiro, Svetlana Heyte, Paul Sébastien, Thierry Roisnel, Jean‐François Carpentier, Evgueni Kirillov,

Organometallic Complex Synthesis and Catalysis

Abstract A series of in situ‐prepared catalytic systems incorporating Ru II 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)(PPh 3 ) 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 % H 2 O vs. HSiEt 3 ). Possible mechanisms are discussed.