- Copper-diphosphine complex catalysts for N-formylation of amines under 1 atm of carbon dioxide with polymethylhydrosiloxane
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N-formylation of a wide range of amines proceeded using copper-diphosphine complexes as homogeneous catalysts with polymethylhydrosiloxane (PMHS) under 1 atm of CO2. In the reaction of piperidine, for example, the turnover number (TON) reached 11700 in 23 h with 90% yield of the formylated product. This TON value is much higher than those of the reported catalysts for the formylation of amines under 1 atm of CO2 with hydrosilanes. The Cu complexes with phosphines having ortho-phenylene structures acted as good ligands for the formylation, as compared to a bidentate ligand connected with a propyl chain and a monodentate ligand. Among these diphosphines, ligands with alkyl functionalities, such as isopropyl and cyclohexyl groups, produced better results than the phenyl group. Not only cyclic secondary amines, but also linear secondary amines and aromatic and aliphatic primary amines were found to be reactive substrates. In the case of 2,2,6,6-tetramethylpiperidin-4-amine, the formylation proceeded regioselectively. A catalytic reaction pathway was proposed from a separate experiment using [Me2NCO2] [Me2NH2]. The Royal Society of Chemistry 2013.
- Motokura, Ken,Takahashi, Naoki,Kashiwame, Daiki,Yamaguchi, Sho,Miyaji, Akimitsu,Baba, Toshihide
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p. 2392 - 2396
(2013/09/02)
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- Rutheniumcluster als Katalysatoren fuer die Carbonylierung von cyclischen Aminen
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The tri- and tetra-nuclear ruthenium clusters Ru3(CO)12, - and - have been found to catalyse the carbonylation of cyclic amines such as piperidine, 3-methylpiperidine, pyrrolidine, heptamethylene imine, morpholine and piperazine to give the corresponding formamides.The catalytic reaction works with only carbon monoxide or a mixture of carbon dioxide and hydrogen.In the case of the neutral catalyst precursor, carbamoyl clusters of the type (μ2-H)Ru3(CO)10(μ2,η2-OCNR2) have been isolated from the reaction mixture.
- Suess-Fink, Georg,Langenbahn, Meinhard,Jenke, Thomas
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p. 103 - 110
(2007/10/02)
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- Silver(I)-catalyzed Oxidation of Cyclic Secondary Amines with Peroxodisulphate
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Oxidation of Piperidines, pyrrolidine, azetidine, perhydroazepine, and perhydroazocine with aqueous alkaline sodium peroxodisulphate in the presence of silver nitrate gave 1,1'-bipiperidines, a trimer of 1-pyrroline, 1,1'-biazetidine, 1,1'-biperhydroazepine together with 1-formylperhydroazepine, and 1-formylperhydroazocine, respectively.
- Ogawa, Keiichiro,Nomura, Yujiro,Takeuchi, Yoshito,Tomoda, Shuji
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p. 3031 - 3036
(2007/10/02)
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