Thorsten Rosner

Enantioselective hydrogenation of olefins with phosphinooxazoline-iridium catalysts.

Cationic iridium complexes with chiral phosphinooxazoline ligands are efficient catalysts for the enantioselective hydrogenation of olefins. The complexes are readily prepared, air-stable, and easy to handle. In contrast to chiral rhodium- and ruthenium-phosphine catalysts, they do not require the presence of a polar coordinating group near the C=C bond. In the hydrogenation of unfunctionalized trisubstituted 1,2-diaryl-olefins, high enantioselectivities of >95% ee with full conversion and turnover frequencies of >7,000 h-1 can be achieved, using 0.1 mol% of catalyst with tetrakis[3, 5-bis(trifluoromethyl)phenyl]borate (TFPB or BARF) as the counterion. The corresponding hexafluorophosphate or tetrafluoroborate salts give low conversion due to deactivation of the catalyst during the reaction. Substrates with polar substituents such as allylic alcohols, on the other hand, afford better results with the hexafluorophosphate salts.

Kinetic Influences on Enantioselectivity for Non‐Diastereopure Catalyst Mixtures

Different kinetic rate laws were observed for two diastereomeric catalysts which separately gave opposite enantioselectivities in the asymmetric hydrogenation of the dimethyl ester of itaconic acid. In reactions carried out using an equal mixture of the two catalysts, a conversion-dependent enantioselectivity was predicted from the separate reaction-rate data, in agreement with the experimentally observed final enantioselectivity of 54.8 % ee (see diagram).

Mono-Oxidation of Bidentate Bis-phosphines in Catalyst Activation: Kinetic and Mechanistic Studies of a Pd/Xantphos-Catalyzed C–H Functionalization

Kinetic, spectroscopic, crystallographic, and computational studies probing a Pd-catalyzed C-H arylation reaction reveal that mono-oxidation of the bis-phosphine ligand is critical for the formation of the active catalyst. The bis-phosphine mono-oxide is shown to be a hemilabile, bidentate ligand for palladium. Isolation of the oxidative addition adduct, with structural elucidation by X-ray analysis, showed that the mono-oxide was catalytically competent, giving the same reaction rate in the productive reaction as the Pd(II)/xantphos precursor. A dual role for the carboxylate base in both catalyst activation and reaction turnover was demonstrated, along with the inhibiting effect of excess phosphine ligand. The generality of the role of phosphine mono-oxide complexes in Pd-catalyzed coupling processes is discussed.

Kinetische Einflüsse auf die Enantioselektivität von nichtdiastereomerenreinen Katalysatormischungen

Unterschiedliche Geschwindigkeitsgesetze wurden fur zwei diastereomere Katalysatoren gefunden, die einzeln eingesetzt zu entgegengesetzten Enantioselektivitaten bei der asymmetrischen Hydrierung von Itaconsauredimethylester fuhrten. Mit einer Mischung aus gleichen Teilen der beiden Katalysatoren wurde anhand der Daten der separaten Reaktionen eine umsatzabhangige Enantioselektivitat vorhergesagt, die mit der experimentell bestimmten Enantioselektivitat von 54.8% ubereinstimmt (siehe Diagramm).