A penny saved is a penny earned: The use of propylene carbonate as the solvent in iridium‐catalyzed hydrogenations of nonfunctionalized olefins allows efficient catalyst recycling through the formation of two‐phase mixtures with nonpolar solvents such as n‐hexane. In the picture, the hydrogenated tetrahydronaphthalene derivative is extracted into the hydrocarbon phase.
Best aminated feature: Catalytic transformation of alcohols to amines is a fundamental transformation in synthetic organic chemistry. A general salt‐free Ir‐catalyzed amination of aliphatic alcohols and diols has been developed, which gives amino alcohols with high selectivity. By use of an Ir–pincer chlorodihydride complex, usually applied for the transfer hydrogenation of ketones, simple monoalcohols are aminated with excellent yields.
A new multi-step synthesis of the lipid-lowering agent rosuvastatin, involving two homogeneously catalyzed reaction steps, is described. The key building block, N-[4-(4-fluorophenyl)-5-formyl-6-isopropylpyrimidin-2-yl]-N-methylmethanesulfonamide (2), was prepared by Pd-catalyzed formylation with CO/H 2 (1:1, 50 bar, phosphane ligand/substrate ratio of 1:10). Several alternative pathways for the preparation of 2 were also tested, but were found to be in-
Höhere Überlebenschancen für teure Katalysatoren: Der Einsatz von Propylencarbonat als Lösungsmittel bei der iridiumkatalysierten Hydrierung nichtfunktionalisierter Olefine ermöglicht ein effizientes Katalysatorrecycling durch Bildung von Zweiphasengemischen mit unpolaren Lösungsmitteln wie n‐Hexan.
Standard molar enthalpies of formation in the gaseous state of a series of alkyl 3-methylbut-2-enoates have been obtained from combustion calorimetry and results from the temperature dependence of the vapor pressure measured by the transpiration method. To verify the experimental data, we have performed ab initio calculations of all compounds. Enthalpies of formation derived from the G3MP2 method are in excellent agreement with the experimental results. Quantitative analysis of strain effects in alkyl 3-methylbut-2-enoates was discussed in terms of deviations of deltafH degrees m(g) from the group additivity rules. Energetics of the cis-trans isomerization of carboxylic acid derivatives was studied using G3MP2 and DFT methods. Values of strain and cis-trans corrections derived in this work provide further improvement on the group-contribution methodology for prediction of the thermodynamic properties of compounds relevant to biodiesel.
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