Aminations tricyclohexylphosphine

To a 300 mL Hastelloy-B autoclave was added 31.0 mL (24.5 g, 765 mmol) of methanol, 90.0 mL (70.Og, 378 mmol) of tributyl amine, 33.0 mL (33.8 g, 251 mmol) of 1-chloropinacolone, 14.0 mg (0.019 mmol) of [(cyclohexyl)3P)]2PdCl2, and 28.0 mg (0.1 mmol) of tricyclohexylphosphine. The autoclave was sealed, flushed with carbon monoxide, and pressurized to 30 psi with CO. The autoclave was then heated to 120°C and the pressure was adjusted to 150 psi. The temperature and pressure were maintained using a continuous carbon monoxide feed for 3 h. The mixture was then cooled to yield a two phase reaction product. The entire product mixture (both layers) was diluted with 50.0 mL (39.55 g) of methanol to generate a homogeneous mixture and analyzed by gas chromatography. Variations in the procedure regarding temperature, pressure, catalyst levels (phosphine and Pd) are indicated in the tables and text. 

The best catalysts are usually DABCO 154 or hydroxyquinuclidine 155 among amines and tricyclohexylphosphine 156. Efforts continue to find effective asymmetric catalysts.41 Examples with acrylates, enolisable aldehydes, and the amine catalysts are 158 and 159. 

Here L4 = a quadridentate Schiff base (NNOO ligating atoms) or (en>2, and the base = (substituted) py or an aliphatic amine. A kinetic study of the reaction of [Co(acacen)(NO)] (13) with oxygen in the presence of one of a number of bases, including (substituted) pyridines, imidazole, aliphatic amines, and phosphines, showed that the rate depends on the basicity of the added base except when steric hindrance becomes important, as, for example, when the added base is tricyclohexylphosphine. Rates were also determined for the reactions of [Co(salen)(NO)] (14), [Co(sacsacen)(NO)] (15), [Co(benacen)-(NO)] (16), and [Co(Me2dtc)a(NO)] (17) with oxygen in the presence of... 

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