Recent developments in enantioselective yttrium-catalyzed transformations

Pellissier, Hélène

doi:10.1016/j.ccr.2016.06.017

Cited by 22 publications

(6 citation statements)

References 215 publications

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“…As one of the most useful classes of intermediates, the asymmetric cyanohydrins have been considered as a very important class of precursors for the synthesis of chiral organic species such as natural and pharmaceutical compounds. − In this context, the well-established biocatalysts, chiral inorganic and organic catalyst promoted enantioenriched cyanohydrin synthesis has been the main theme, but in the way of homogeneous catalysis. − As a promising alternative to homogeneous catalysis, heterogeneous catalysis is much more eco-friendly and offers cost savings due to the reusability of the catalysts. − …”

Section: Introductionmentioning

confidence: 99%

Homochiral BINAPDA-Zr-MOF for Heterogeneous Asymmetric Cyanosilylation of Aldehydes

Jin

Zhao

et al. 2019

Inorg. Chem.

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A new homochiral BINAPDA-Zr-MOF was prepared by a new chiral organic linker of (R)-4,4′-(6,6′-dichloro-2,2′-diethoxyl-[1,1′-binaphthalene]-4,4′-diyl)dibenzoic acid (R -L) and ZrCl4 under solvothermal conditions. Its structure was determined by Pawley refinement on the basis of the measured PXRD pattern determined for BINAPDA-Zr-MOF, and it showed that the obtained chiral MOF crystallized in the F23 space group with the same topological structure as that of UiO-66. The obtained BINAPDA-Zr-MOF can be a very active catalyst to catalyze aldehyde cyanosilylation. In addition, the chiral BINAPDA-Zr-MOF was a typical solid catalyst, which was proved by a hot leaching test; moreover, it could be reused at least five times without loss of its catalytic activity and enantioselectivity.

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Section: Introductionmentioning

confidence: 99%

Homochiral BINAPDA-Zr-MOF for Heterogeneous Asymmetric Cyanosilylation of Aldehydes

Jin

Zhao

et al. 2019

Inorg. Chem.

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“…Young's tap. Solutions were subsequently degassed by two freezepump-thaw cycles using a Schlenk line before reacting with H 2 (3 bar) for 30 mins at room temperature to form [Ir(H) 2 (k 2pyruvate)(DMSO)(IMes)] in situ, which was indicated by a colour change from pale yellow to colourless and was confirmed from characteristic 1 H NMR hydride resonances. [39,49] The H 2 atmosphere was then replaced with pH 2 (3 bar) and shaken vigorously for 30 seconds in a mu metal shield.…”

Section: Complexmentioning

confidence: 99%

“…Yttrium is situated in the d‐block of the periodic table and many organoyttrium species have been reported to catalyse a wide range of organic transformations, including hydroaminations, Michael additions, epoxidations and many others [1] . It is also known to form stable complexes in aqueous media with polydentate polyaminocarboxylate ligands in a fashion analogous to many lanthanides [2–10] .…”

Section: Introductionmentioning

confidence: 99%

In Situ Ternary Adduct Formation of Yttrium Polyaminocarboxylates Leads to Small Molecule Capture and Activation

Tickner

Platas‐Iglesias

Duckett

et al. 2022

Chemistry A European J

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In this work the chemistry of yttrium complexes is exploited for small molecule capture and activation. Nuclear magnetic resonance (NMR) and density functional theory (DFT) studies were used to investigate the in situ formation of solution state ternary yttrium-acetate, yttrium-bicarbonate, and yttrium-pyruvate adducts with a range of polyaminocarboxylate chelates. These studies reveal that [Y(DO3A)(H 2 O) 2 ] (H 3 DO3A -1,4,7,10-tetraazacyclododecane-1,4,7-tricarboxylic acid) and [Y(EDTA)(H 2 O) 2 ] À (H 4 EDTA -ethylenediaminetetraacetic acid) are able to form ternary adducts with bicarbonate and pyruvate. In the latter, unusual decarboxylation of pyruvate to form acetic acid and CO 2 was observed and further studied using SABRE-hyperpolarised 13 C NMR (SABREsignal amplification by reversible exchange) to provide information about the reaction timescale and lifetime of intermediates involved in this conversion. The work presented demonstrates that yttrium complexes can capture and activate small molecules, which may lead to novel and useful applications of this metal in catalysis and medical imaging.

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“…Asymmetric metal catalysis has emerged as an important tool for the development of chiral molecules with high molecular complexity with simple operational one-pot procedures, atom efficiency, and mild reaction conditions. − We have reported the asymmetric scandium(III)-catalyzed [3 + 2] annulation of alkylidene oxindoles and isatins with allylsilane and allenylsilane nucleophiles. − The scandium(III)–PyBox/BArF (PyBox: pyridine-2,6-bis(oxazoline); BArF: tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) complex is a powerful catalyst system, demonstrating robust activity in a variety transformations and with potential application toward further synthetic applications. − However, our previous studies provided an incomplete picture of the active catalyst complex that we were interested in investigating further. We elected to study the Sc(OTf) 2 -( R , S )-inda-PyBox ( L1 )/BArF complex using the [3 + 2] annulation reaction of allylsilanes 2a with alkylidene oxindole 1a (Scheme ).…”

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confidence: 99%

Ligand-Accelerated Catalysis in Scandium(III)-Catalyzed Asymmetric Spiroannulation Reactions

et al. 2022

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A mechanism for the scandium-catalyzed asymmetric allylsilane annulation reaction is proposed and supported by reaction heat flow calorimetry, NMR, and in situ infrared spectroscopy. The nature of a scandium(III)–PyBox/BArF catalyst is probed using reaction calorimetric analysis, which reveals a complex interplay between in-solution and precipitated catalyst species. The scandium(III)–PyBox/BArF catalyst is minimally soluble until the addition of a bidentate electrophile. The optimal reaction rate is dependent on precomplexation of the catalyst, order of complexation of the catalyst components, and delayed addition of nucleophile. The formation of the active catalyst proceeds through a bimolecular combination of scandium(III) with a BArF anion, followed by complexation with PyBox ligand, where the ligand-dependent rate and selectivity are observed. Notably, ligand-accelerated catalysis is observed, attributed to the ligand reducing off-cycle oligomerization of allylsilane. The role of BArF is discussed with a specific focus on the source of counterion in the reaction rate and enantioselectivity. We also report the formation of a mechanistically relevant fused tetrahydropyranindole produced upon the reaction of an allylsilane with alkylidene oxindole. In situ infrared spectroscopy demonstrates ligand-dependent acceleration where sterically demanding ligands perform with a faster relative reaction rate.

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Recent developments in enantioselective yttrium-catalyzed transformations

Cited by 22 publications

References 215 publications

Homochiral BINAPDA-Zr-MOF for Heterogeneous Asymmetric Cyanosilylation of Aldehydes

Homochiral BINAPDA-Zr-MOF for Heterogeneous Asymmetric Cyanosilylation of Aldehydes

In Situ Ternary Adduct Formation of Yttrium Polyaminocarboxylates Leads to Small Molecule Capture and Activation

Ligand-Accelerated Catalysis in Scandium(III)-Catalyzed Asymmetric Spiroannulation Reactions

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