A Smart Heterogeneous Catalyst for Efficient, Chemo- and Stereoselective Hydrogenation of 3-Hexyn-1-ol

We examine the easy preparation of mono-and bi-metallic heterogeneous catalysts with low Pd and Cu contents on alumina and provide a detailed study of many reaction parameters in the catalyzed selective semihydrogenation of 3-hexyn-1-ol to (Z)-3-hexen-1-ol, a very important fragrance with an herbaceous note. In particular, two different protocols of Pd catalyst preparation, substrate/catalyst molar ratio, the effect of time and temperature, introduction of some additives to the reaction mixture, and the nature of the solvent were investigated. These factors are not independent variables. The results show that it is possible to control the reaction outcome to obtain the target (Z)-alkenol using different experimental conditions. The best result, as an appropriate compromise between conversion and selectivity, may be obtained by working with a very high substrate/catalyst molar ratio (>6000/1), with one type of Pd catalyst, in a short time (about 150 min) at 60◦C

Improved Process for the Synthesis of 3-(3-Trifluoromethylphenyl)propanal for More Sustainable Production of Cinacalcet HCl

Cinacalcet (I), sold as hydrochloride salt, is a calcimimetic drug which has been approved for the treatment of secondary hyperparathyroidism in patients with chronic renal disease and for the treatment of hypercalcemia in patients with parathyroid carcinoma. Here, an improved method for the synthesis of 3-(3-trifluoromethylphenyl)propanal (II), a key intermediate for the preparation of I, is described. The protocol required a Mizoroki–Heck cross-coupling reaction between 1-bromo- 3-(trifluoromethyl)benzene and acroleine diethyl acetal, catalyzed by Pd(OAc)2 in the presence of nBu4NOAc (tetrabutylammonium acetate), followed by the hydrogenation reaction of the crude mixture of products in a cascade process. Palladium species, at the end of the reaction, were efficiently recovered as Pd/Al2O3. The procedure was developed under conventional heating conditions as well as under microwave-assisted conditions. The obtained mixture of 1-(3,3-diethoxypropyl)-3- (trifluoromethyl)benzene (III), impure for ethyl 3-(3-trifluoromethylphenyl) propanoate (IV), was finally treated, under mild conditions, with potassium diisobutyl-tert-butoxyaluminum hydride (PDBBA) to obtain after hydrolysis 3-(3-trifluoromethylphenyl)propanal (II), in an excellent overall yield and very high purity. Microwave conditions permitted a reduction in reaction times without affecting selectivity and yield. The final API was obtained through reductive amination of (II) with (R)-(+)-1-(1-naphthyl)ethylamine (V) using a catalyst prepared by us with a very low content of precious metal

Selective reduction of halo-nitro aromatic compounds using [Rh]/DHTANa as catalyst in an aqueous bi-phase system

The use of water as co-solvent for biphasic reactions and of easily recyclable water-soluble catalysts are highly desirable for the realization of greener processes. The selective reduction of halo nitroarenes to the corresponding haloanilines is a very important industrial transformation for the production of agrochemicals, pigments, bactericides and pharmaceuticals and is not easy to obtain. The application of a water soluble catalyst, prepared by rhodium species and a cheap thioligand, in the hydrogenation of some halonitroarenes is here described. Excellent conversions, good recyclability of the catalytic species embedded in the aqueous phase and very high selectivity are demonstrated. (C) 2016 Elsevier B.V. All rights reserved

Sintesi di derivati indolici farmacologicamente attivi mediante una sequenza tandem di idroformilazione-riduzioneciclizzazione

Molti principi attivi per farmaci antiipertensivi, antitumorali e antivirali contengono nella loro molecola elementi strutturali di natura indolica.1-3 Durante lo studio sull'idroformilazione di particolari substrati olefinici vinilaromatici aventi un sostituente -NO2 o -NH2 in posizione orto, abbiamo confrontato i risultati ottenuti su gli esteri metilici dell'acido o-nitro- (1) e oamminocinnamico (2) sottoposti a reazione di oxosintesi, catalizzata da vari complessi di rodio

An easily recoverable and recyclable homogeneous polyester-based Pd catalytic system for the hydrogenation of α,β-unsaturated carbonyl compounds

Homogeneous catalysis is an efficient tool to carry out hydrogenation processes but the major drawback is represented by the separation of the expensive catalyst from the product mixture. In this view we prepared a polyester-based Pd catalytic system that offers the advantages of both homogenous and heterogeneous catalyses: efficacy, selectivity and recyclability. Here its application in the hydrogenation of selected alpha,beta-unsaturated carbonyl compounds is described

Aqueous biphasic treatment of some nitrocompounds with hydrogen in the presence of a biogenerated Pd-polysaccharide

A strain of Klebsiella oxytoca BAS-10, known to produce a specific exopolysaccharide (EPS), when grown aerobically in static mode in the presence of Pd(NO3)(2), generated the species Pd-EPS that was used as catalyst precursor in the aqueous biphasic treatment of some nitrocompounds with hydrogen. Nitrobenzene was hydrogenated to aniline with almost quantitative yields and the catalyst, embedded in the aqueous phase, was used with success and with near the same efficiency in three recycling experiments. In the case of 1-iodo-4-nitrobenzene only nitrobenzene was obtained while the unsaturated nitro compound beta-methyl-beta-nitrostyrene afforded both the corresponding oxime and the saturated nitro derivative