22644-27-5Relevant academic research and scientific papers
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
Me-AnilaPhos: a new chiral phosphine-phosphoramidite ligand for a highly efficient Rh-catalyzed asymmetric olefin hydrogenation
Vallianatou, Kalliopi A.,Kostas, Ioannis D.,Holz, Jens,B?rner, Armin
, p. 7947 - 7950 (2006)
A cationic rhodium(I) complex with a novel chiral phosphine-phosphoramidite ligand based on 2-diphenylphosphino-N-methylaniline and R-BINOL moieties has been synthesized. The complex provided remarkably high activity and enantioselectivity in the asymmetr
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
New ionic phosphite ligands: Synthesis and application in asymmetric Rh-catalyzed hydrogenation
Lyubimov,Petrovskii,Davankov
, p. 528 - 531 (2009)
A series of chiral ionic phosphite-type ligands bearing pyridinium and imidazolium fragments were prepared. Testing of these ligands in Rh-catalyzed asymmetric hydrogenation of dimethyl itaconate and methyl 2-acetamidoacrylate resulted in 95% ee of the products with 100% conversion of the reactants.
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
BINOL-derived diphosphoramidites bearing unsymmetrical 1,2-diamine link and their application in asymmetric catalysis
Gavrilov, Konstantin N.,Shiryaev, Alexei A.,Chuchelkin, Ilya V.,Zheglov, Sergey V.,Rastorguev, Eugenie A.,Davankov, Vadim A.,Boerner, Armin
, p. 1052 - 1057 (2012)
New P,P-bidentate diastereomeric diphosphoramidite chiral ligands with mixed stereogenic elements and a C1 backbone symmetry have been prepared from (Sa)- and (Ra)-1,1′-binaphthyl-2, 2′-diol (BINOL) and (S)-N-benzyl-1-(pyr
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],
Using Data Science To Guide Aryl Bromide Substrate Scope Analysis in a Ni/Photoredox-Catalyzed Cross-Coupling with Acetals as Alcohol-Derived Radical Sources
Doyle, Abigail G.,Gandhi, Shivaani S.,Jiang, Shutian,Kariofillis, Stavros K.,Martinez Alvarado, Jesus I.,?urański, Andrzej M.
supporting information, p. 1045 - 1055 (2022/01/19)
Ni/photoredox catalysis has emerged as a powerful platform for C(sp2)–C(sp3) bond formation. While many of these methods typically employ aryl bromides as the C(sp2) coupling partner, a variety of aliphatic radical sources have been investigated. In principle, these reactions enable access to the same product scaffolds, but it can be hard to discern which method to employ because nonstandardized sets of aryl bromides are used in scope evaluation. Herein, we report a Ni/photoredox-catalyzed (deutero)methylation and alkylation of aryl halides where benzaldehyde di(alkyl) acetals serve as alcohol-derived radical sources. Reaction development, mechanistic studies, and late-stage derivatization of a biologically relevant aryl chloride, fenofibrate, are presented. Then, we describe the integration of data science techniques, including DFT featurization, dimensionality reduction, and hierarchical clustering, to delineate a diverse and succinct collection of aryl bromides that is representative of the chemical space of the substrate class. By superimposing scope examples from published Ni/photoredox methods on this same chemical space, we identify areas of sparse coverage and high versus low average yields, enabling comparisons between prior art and this new method. Additionally, we demonstrate that the systematically selected scope of aryl bromides can be used to quantify population-wide reactivity trends and reveal sources of possible functional group incompatibility with supervised machine learning.
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.
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.
