Modular optimization of enantiopure epoxide-derived P,S-ligands for rhodium-catalyzed hydrogenation of dehydroamino acids

The optimization of P,S-ligands derived from enantiopure (2S,3S)-phenylglycidol for asymmetric rhodium-catalyzed hydrogenation of dehydroamino esters is described. The exceptionally high modular character of the (2S,3S)-phenylglycidol platform is demonstrated by systematic modification of the ether and thioether moieties, the skeletal aryl substituent and the stereo and regiochemistry of the ligands. An experimentally useful method for the monitoring of hydrogenation reactions is also described and used for obtaining relevant data of the catalytic systems studied.     

Reversing the stereoselectivity of the intermolecular Pauson-Khand reaction: formation of endo-fused norbornadiene adducts

[reaction: see text] An unprecedented endo-selective and regioselective intermolecular Pauson-Khand reaction takes place when heterobimetallic (Mo-Co) complexes derived from N-(2-alkynoyl)oxazolidinones or sultams are heated in the presence of norbornadiene.     

The Reactivity Of singlet carbenes. An ab initio study

The energy barriers for the addition to ethylene of a series of carbenes have been calculated at an ab initio level. using the STO-3G and 3-21G basis sets. It is shown that the usual extrapolation of experiment results, which predicts that the reactivity of carbenes decreases when increasing its nucleophilic character, is not valid.     

Single and double metallic layer-containing ruthenium dendrimers. Synthesis and catalytic properties

The reaction of a series of phosphanyl-terminated carbosilane dendrimers displaying only one phosphorus ligand per arm with [RuCl(2)(p-cymene)](2) resulted in the grafting of RuCl(p-cymene) moieties on the periphery of the dendrimer. In these species, the chloride ligand is easily displaced by the organic bases pyridine, 4-cyanopyridine and 4,4[prime or minute]-bipyridine to afford new cationic metallodendrimers. NMR studies have confirmed the chirality of the ruthenium centre. The species containing 4,4[prime or minute]-bipyridine reacts through the uncoordinated pyridyl nitrogen with a new equivalent of [RuCl(2)(p-cymene)](2) or [RhCl(CO)(2)](2) to lead to homo- or hetero-bimetallic layer-containing dendrimeric systems. The ruthenodendrimers were tested as catalysts in the transfer hydrogenation of cyclohexanone by propan-2-ol and their activity compared with that of some analogous mononuclear ruthenium(ii) complexes.