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.
Mechanistically Guided One Pot Synthesis of Phosphine-Phosphite and Its Implication in Asymmetric Hydrogenation
Chikkali, Samir H.,Kumar, Pawan,Kumar, Rohit,Pandey, Swechchha,Sen, Anirban,Vanka, Kumar,Vipin Raj, K.
supporting information, (2022/01/11)
Although hybrid bidentate ligands are known to yield highly enantioselective products in asymmetric hydrogenation (AH), synthesis of these ligands is an arduous process. Herein, a one pot, atom-economic synthesis of a hybrid phosphine-phosphite (L1) is reported. After understanding the reactivity difference between an O-nucleophile versus C-nucleophile, one pot synthesis of Senphos (L1) was achieved (72 %). When L1 was treated with [Rh], 31P NMR revealed bidentate coordination to Rh. Senphos, in the presence of rhodium, catalyzes the AH of Methyl-2-acetamido-3-phenylacrylate and discloses an unprecedented turn over frequency of 2289, along with excellent enantio-selectivity (92 %). The generality is demonstrated by hydrogenating an array of alkenes. The AH operates under mild conditions of 1–2 bar H2 pressure, at room temperature. The practical relevance of L1 is demonstrated by scaling-up the reaction to 1 g and by synthesizing DOPA, a drug widely employed for the treatment of Parkinson's disease. Computational insights indicate that the R isomer is preferred by 3.8 kcal/mol over the S isomer.
