Chinoin Zrt.

A new Pd/MgLa mixed oxide and the known Pd/MgAl hydrotalcite catalysts were applied and recycled successfully in catalytic transfer hydrogenation reactions in ionic liquidsSome α,β-unsaturated carboxylic acid derivatives were hydrogenated in excellent yields.The catalysts were recycled without significant loss of activity.Besides that, a number of halogenated aromatic compounds were dehalogenated under similar catalytic transfer conditions.

The formation of enamino aldehydes and acrylamides from tertiary propargylamine N-oxides in protic media can be interpreted as a novel prototropic rearrangement.The proposed rearrangement mechanism is supported by isotopic labeling experiments and by relevant literature data.

A facile convergent total synthesis of the selective, potent, and orally active V2 non-peptide antagonist, SR-121463, was developed by modification of the discovery route. One of the late intermediates, the sulfonyl chloride 1, was synthesized from 3-hydroxybenzoic acid (19) by regioselective sulfonation, O-methylation and amidation in four steps. Another late intermediate, indolin-2-one 2, was prepared from p-phenetidine (8) through the indolin-2-one 16, where the cyclohexanone moiety of 27 was introduced into the active 3-methylene group of 16 by sequential transformation using methyl acrylate and KOtBu. After formation of the cyclic ketal moiety of 13, its ring-opening was achieved by using NaBH4 in the presence of CCl3COOH. The morpholino group in 2 was introduced in accordance with the discovery approach, starting from the 2-hydroxyethoxy derivative 14 through the tosyloxy derivative 15 with morpholine in a one-pot reaction. In this way, the indolin-2-one 2 was synthesized from 8 in six steps. Finally, acylation of the indolin-2-one 2 was achieved with the sulfonyl chloride 1 in the presence of KOtBu in dimethyl sulfoxide (DMSO) at room temperature. This synthetic route proved to be applicable for the large-scale synthesis of SR-121463.