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Ruthenium‐Catalyzed Coupling Reactions of CO 2 with C 2 H 4 and Hydrosilanes towards Silyl Esters
Author(s) -
Kunihiro Kana,
Heyte Svetlana,
Paul Sébastien,
Roisnel Thierry,
Carpentier JeanFrançois,
Kirillov Evgueni
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202005083
Subject(s) - ruthenium , chemistry , triethylsilane , catalysis , phosphine , propionate , silylation , acrylate , medicinal chemistry , disproportionation , methyl acrylate , selectivity , crotonaldehyde , ethylene , polymer chemistry , organic chemistry , copolymer , polymer
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.