Clathrochelates meet phosphorus: thiophosphorylation of Fe(II) dichloroclathrochelate precursor, synthesis of N,S-donor macrobicyclic ligands and their Pd(II) complexes as potent catalysts of Suzuki cross-coupling reaction.

Nucleophilic substitution of an iron(ii) dichloroclathrochelate with diphenylphosphine sulfide under PTC afforded a monophosphorylated cage complex. This precursor undergoes further nucleophilic substitution with mono- and diamines giving P,N-substituted mono- and bis-clathrochelates; those with thiophosphoryl and pyridyl groups were used as N,S-donor macrobicyclic ligands toward the palladium(ii) ion. In the resulting Pd,Fe-binuclear 1 : 1 complexes, the clathrochelate moieties retain the geometry, characteristic of low-spin iron(ii) complexes, with a minor distortion caused by intramolecular interactions. The Pd(2+) ion has a twisted square-planar N2SCl-environment. The complexes thus obtained proved to be efficient catalysts of the Suzuki cross-coupling reaction.

The use of phosphite-type ligands in the Ir-catalyzed asymmetric hydrogenation of heterocyclic compounds.

A series of chiral phosphite-type ligands was tested in asymmetric Ir-catalyzed hydrogenation of quinolines and 2,4,5,6-tetrahydro-1H-pyrazino(3,2,1-j,k)carbazole. Hydrogenation of quinaldine hydrochloride provided superior enantioselectivity up to 65% ee compared to quinaldine free base. The ligands were tested for the first time in the asymmetric Ir-Ircatalyzed hydrogenation of 2,4,5,6-tetrahydro-1H-pyrazino(3,2,1-j,k)carbazole yielding the antidepressant drug, pirlindole.

Application of a new amidophosphite ligand to Rh-catalyzed asymmetric hydrogenation of ß-dehydroamino acid derivatives in supercritical carbon dioxide: activation effect of protic Co-solvents.

New chiral amidophosphite ligand was synthesized and tested in the Rh-catalyzed asymmetric hydrogenation of (Z)-ß-(acylamino)acrylates in protic solvents and supercritical carbon dioxide (scCO(2) ) The catalytic performance is affected greatly by the acidity of the solvents. Better enantioselectivity (up to 88% ee) was achieved in scCO(2) containing 1,1,1,3,3,3-hexafluoro-2-propanol, compared to neat protic solvents.

Chiral phosphites derived from carboranes: electronic effect in catalytic asymmetric hydrogenation.

A series of new fine-tunable monodentate phosphite and phosphoramidite ligands based on carboranes have been synthesized and used for asymmetric Rh-catalyzed hydrogenation of prochiral olefins with the result of up to 99.8% ee. Dependence of the enantioselectivity on the electron-withdrawing or electron-donating properties of the carboranyl substituent has been studied.

Novel P,N-bidentate phosphite ligands in asymmetric catalysis.

Results achieved by the authors in the synthesis of chiral P,N-phosphite ligands are summarized. Three groups of new chiral P,N-phosphites are discussed, namely, ligands derived from 1,1'-bi-2-naphthol, ligands possessing an acyclic phosphorus center, and P*-chiral ligands derived from (S)-2-anilinomethylpyrrolidine. An overview of complexation of the ligands with Rh(I) and Pd(II) precursors is given. Accessibility and stability of chiral phosphite ligands possessing acyclic phosphorus was analyzed for the first time along with their efficiency in terms of stereoselectivity. The title ligands are shown to be highly efficient in the Pd-catalyzed allylic alkylation (up to 85% ee) and, especially, allylic sulfonylation (up to 97% ee) reactions in certain cases outperformed all known catalytic systems.