22644-27-5Relevant articles and documents
The use of new carboranylphosphite ligands in the asymmetric Rh-catalyzed hydrogenation
Lyubimov, Sergey E.,Kuchurov, Ilya V.,Tyutyunov, Andrey A.,Petrovskii, Pavel V.,Kalinin, Valery N.,Zlotin, Sergei G.,Davankov, Vadim A.,Hey-Hawkins, Evamarie
, p. 419 - 421 (2010)
A series of new monodentate phosphite ligands based on carboranes have been synthesized and used for asymmetric Rh-catalyzed hydrogenation of prochiral olefins in CH2Cl2 with the result of up to 99.5% ee. High reactivities (100% conv
Chiral carborane-derived thiophosphites: A new generation of ligands for Rh-catalyzed asymmetric hydrogenation
Lyubimov, Sergey E.,Davankov, Vadim A.,Petrovskii, Pavel V.,Hey-Hawkins, Evamarie,Tyutyunov, Andrey A.,Rys, Evgeny G.,Kalinin, Valery N.
, p. 3689 - 3691 (2008)
A new class of chiral monodentate ligands - carborane-containing thiophosphites have been synthesized and tested in the Rh-catalyzed asymmetric hydrogenation of prochiral olefins with the result of up to 99% ee. The dependence of the enantioselectivity on
Phosphorodiamidite derivatives of 1,1'-bi-2-naphthol containing stereogenic phosphorus atoms as ligands in enantioselective catalysis
Gavrilov,Safronov,Rastorguev,Groshkin,Zheglov,Shiryaev,Maksimova,Petrovskii,Davankov,Reetz
, p. 434 - 440 (2010)
P*-Mono- and P*,P*-bidentate phosphorodiamidites containing the (Sa)-1,1'-binaphthyl core and 1,3,2-diazaphospholidine rings were synthesized. The use of these compounds in the rhodium-catalyzed asymmetric hydrogenation, as well as in the palla
Chiral supported ionic liquid phase (CSILP) catalysts for greener asymmetric hydrogenation processes
Podolean, Iunia,Hardacre, Christopher,Goodrich, Peter,Brun, Nicolas,Backov, Rénal,Coman, Simona M.,Parvulescu, Vasile I.
, p. 63 - 73 (2013)
Chiral supported ionic liquid phase (CSILP) catalysts were prepared by physical adsorption (within highly porous carbons or mesoporous silica) of Ir, Ru and Rh complexes as IrCl(COD)-(S,S)-BDPP, [IrCl-(S)-BINAP]2, RuCl(p-cymene)[(S,S)-Ts-DPEN],
A robust and stereocomplementary panel of ene-reductase variants for gram-scale asymmetric hydrogenation
Nett, Nathalie,Duewel, Sabine,Schmermund, Luca,Benary, Gerrit E.,Ranaghan, Kara,Mulholland, Adrian,Opperman, Diederik J.,Hoebenreich, Sabrina
, (2021/01/25)
We report an engineered panel of ene-reductases (ERs) from Thermus scotoductus SA-01 (TsER) that combines control over facial selectivity in the reduction of electron deficient C[dbnd]C double bonds with thermostability (up to 70 °C), organic solvent tolerance (up to 40 % v/v) and a broad substrate scope (23 compounds, three new to literature). Substrate acceptance and facial selectivity of 3-methylcyclohexenone was rationalized by crystallisation of TsER C25D/I67T and in silico docking. The TsER variant panel shows excellent enantiomeric excess (ee) and yields during bi-phasic preparative scale synthesis, with isolated yield of up to 93 % for 2R,5S-dihydrocarvone (3.6 g). Turnover frequencies (TOF) of approximately 40 000 h?1 were achieved, which are comparable to rates in hetero- and homogeneous metal catalysed hydrogenations. Preliminary batch reactions also demonstrated the reusability of the reaction system by consecutively removing the organic phase (n-pentane) for product removal and replacing with fresh substrate. Four consecutive batches yielded ca. 27 g L?1 R-levodione from a 45 mL aqueous reaction, containing less than 17 mg (10 μM) enzyme and the reaction only stopping because of acidification. The TsER variant panel provides a robust, highly active and stereocomplementary base for further exploitation as a tool in preparative organic synthesis.
PHANE-TetraPHOS, the First D2 Symmetric Chiral Tetraphosphane. Synthesis, Metal Complexation, and Application in Homogeneous Stereoselective Hydrogenation
Benincori, Tiziana,Cirilli, Roberto,Pierini, Marco,Rizzo, Simona,Terraneo, Giancarlo,Vaghi, Luca
, p. 2367 - 2374 (2021/06/25)
PHANE-TetraPHOS, a new D2 symmetric tetraphosphane based on the [2.2]paracyclophane scaffold, has been synthesized and characterized. The peculiarity of this system is the presence of four homotopic diphenylphosphane groups, exchangeable through C2 symmetry operations and consequently indistinguishable. Their spatial arrangement allows the simultaneous complexation of two metal atoms. Enantiomeric purity was attained at tetra-phosphane oxide level by fractional crystallization of the diastereomeric adducts obtained from the racemate with enantiopure dibenzoyltartaric acids. Alkaline treatment of diastereomerically pure adducts followed by exhaustive P?O groups reduction with HSiCl3 gave both PHANE-TetraPHOS antipodes in an enantiopure state. They were tested as rhodium ligands in the homogeneous enantioselective hydrogenation of some benchmark unsaturated compounds. Catalytic activity and enantiodiscrimination ability were found comparable to those exhibited by the complexes of the parent bidentate ligand PHANEPHOS, but only half a mole of precious chiral ligand was employed.