Enantioseparation of amino acid and mandelic acid enantiomers using Garphos derivatives as chiral extractants

Wang, Hou; Yang, Yanning; Chen, Shuhuan; Xiao, Wenjie; Hu, Kangyu; Zhong, Changyuan; Ouyang, Junying; Liu, Xiong

doi:10.1002/chir.23484

Cited by 5 publications

(6 citation statements)

References 35 publications

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“…For instance, D‐enantiomers are preferentially extracted for Phe, Nphe, and CMA, whereas L‐enantiomers are the preferred enantiomers for Josiphos in extraction of Hphe, Cpheg, and MA. This phenomenon indicates that the stereoconfiguration and electron effect of substrates also play important roles in chiral extraction 27 . The α values of Josiphos‐Pd are all superior to Josiphos‐Cu.…”

Section: Resultsmentioning

confidence: 92%

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Enantioseparation of amino acid and mandelic acid enantiomers using Josiphos‐metal complexes as chiral extractants

Wang

Yang²,

Qin

et al. 2023

Chirality

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The development of new and efficient chiral extractants has always been the research hotspot and difficulty in the field of chiral extraction. Josiphos, a famous ferrocene derivative catalyst, is employed as a chiral extractant in enantioseparation of amino acid and mandelic acid enantiomers. The influences of metal ions, organic solvents, pH of the aqueous solution, extractant concentrations, and extraction temperature on enantioselectivities are systematically studied. The result reveals that Josiphos-Pd has good capabilities to enantioseparate 4-nitro-phenylalanine (Nphe), 3-chloro-phenylglycine (Cpheg), and mandelic acid (MA) with separation factors (α) of 3.30, 2.65, and 2.18, respectively. The pH of the aqueous phase and Josiphos-Pd concentration affect the extraction significantly, whereas extraction temperature shows little influence. After optimizing by response surface method, the mathematical models for extractions are established. And the highest experimental performance factors (pf ) for Nphe, Cpheg, and MA are 0.1843, 0.1335, and 0.08884, respectively.

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Section: Resultsmentioning

confidence: 92%

“…3. 27 The α values of Josiphos-Pd are all superior to Josiphos-Cu. Tetradentate Pd(II) has a planar quadrilateral configuration, whereas tetradentate Cu(I) has a tetrahedral configuration.…”

Section: Optimization Methodsmentioning

confidence: 97%

Enantioseparation of amino acid and mandelic acid enantiomers using Josiphos‐metal complexes as chiral extractants

Wang

Yang²,

Qin

et al. 2023

Chirality

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“…These weakened π-electron and non-π-electron systems may account for the change of the preferred enantiomers. 31 Similar to Phe and Hphe, L-Cpheg is the preferred enantiomer for Mandyphos-10-Pd. However, k D is still bigger than k L when Mandyphos-9-Pd is used as a chiral extractant.…”

Section: Resultsmentioning

confidence: 97%

“…It has been proved that the enantioseparation properties of diphosphinemetal complexes can also be improved by tuning the structures of the parent diphosphines. [31][32][33] For instance, (S)-MeO-BIPHEP derivatives with different dihedral angles (C n TunaPhos, n = 1-6) were synthesized and the influences of dihedral angles on enantioselectivities were investigated in our previous work. 32 The separation factors for (S)-MeO-BIPHEP-metal complexes had been improved significantly by adjusting dihedral angles.…”

Section: Introductionmentioning

confidence: 99%

“…Structural modification is the most frequently used method to optimize the properties of precursor molecules. It has been proved that the enantioseparation properties of diphosphine‐metal complexes can also be improved by tuning the structures of the parent diphosphines 31‐33 . For instance, ( S )‐MeO‐BIPHEP derivatives with different dihedral angles (C n TunaPhos, n = 1–6) were synthesized and the influences of dihedral angles on enantioselectivities were investigated in our previous work 32 .…”

Section: Introductionmentioning

confidence: 99%

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Improvement of the enantioselectivities of Mandyphos‐Pd complexes by introducing groups with different steric and electronic properties

Liu,

Qin,

Wang

et al. 2024

J of Chemical Tech & Biotech

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BackgroundMandyphos‐Pd has been proven to be a good chiral extractant to enantioseparate 3‐chlorophenylglycine enantiomers with a separation factor of 2.64. However, this extractant is not suitable to enantioseparate other amino acids with separation factors below 2.0. The poor versatility has limited its practical application in chiral extraction.RESULTSMandyphos derivatives with different steric and electronic properties were synthesized and their enantioseparation properties toward amino acid and mandelic acid enantiomers were investigated. The results suggested that the substituent groups with different steric properties affect the extraction properties probably by adjusting the angles of tetra‐coordinated palladium complexes. And the substituent groups with different electronic properties affect the extraction properties mainly by adjusting the π‐π interactions/steric hindrance effects between Mandyphos‐Pd and substrates. After optimization, the highest separation factors for phenylalanine, homophenylalanine, 3‐chloro‐phenylglycine, 4‐nitro‐phenylalanine, mandelic acid and 2‐Cl‐mandelic acid are 2.10, 2.77, 3.51, 2.42, 2.24 and 5.19, respectively. The enantioseparation mechanisms revealed that the coordination interactions between metal ions and ‐COO−/‐NH2, π‐π interactions or steric hindrance effects between aryls are the main acting forces in chiral recognition.CONCLUSIONThe enantioselectivities of Mandyphos‐Pd complexes are improved by introducing groups with suitable steric and electronic properties. Structural modification is a useful method to improve the enantioseparation efficiencies of chiral extractants. The results of this work will supply important theoretical guidance and reference for the design and modification of novel diphosphine ligands in future work.This article is protected by copyright. All rights reserved.

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Synthesis and Characterization of Air‐Stable Palladium(II) and Copper(I) Ph‐Garphos Complexes and their Applications to Asymmetric Catalysis

Lorraine,

Green,

Abdur‐Rashid

et al. 2024

ChemistrySelect

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Air‐stable palladium(II) and copper(I) complexes containing the 4,4′,6,6′‐tetramethoxybiphenyl‐2,2′‐diyl)bis(diphenylphosphine) ligands, (R)‐Ph‐Garphos ((R)‐L1) and ((S)‐Ph‐Garphos ((S)‐L1), were synthesized and characterized by 1H‐, 13C‐, and 31P{1H} NMR spectroscopy and elemental analyses. The PdCl2((R)‐Ph‐Garphos) ((R)‐1) and PdCl2((S)‐Ph‐Garphos) ((S)‐1) complexes were assessed for the Suzuki‐Miyaura cross‐coupling of aryl halides with phenylboronic acid under ambient conditions, or naphthyl substrates under reflux. X‐ray crystal structures of the copper complexes revealed that [Cu((R)‐Ph‐Garphos)I] ((R)‐2) crystallized as a three‐coordinate monomer in the orthorhombic space group P212121 whereas [Cu((S)‐Ph‐Garphos)I] ((S)‐2) crystallized as a tetrahedral (μ‐I) dimer in the same crystal system. The synthesis of the analogous [Cu((R)‐Ph‐Garphos)OAc] ((R)‐3) is also described. Complexes (R)‐2 and (R)‐3 were evaluated for the asymmetric hydrosilylation of ketones wherein enantioselectivities of up to 83 % ee were achieved.

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Enantioseparation of amino acid and mandelic acid enantiomers using Garphos derivatives as chiral extractants

Cited by 5 publications

References 35 publications

Enantioseparation of amino acid and mandelic acid enantiomers using Josiphos‐metal complexes as chiral extractants

Enantioseparation of amino acid and mandelic acid enantiomers using Josiphos‐metal complexes as chiral extractants

Improvement of the enantioselectivities of Mandyphos‐Pd complexes by introducing groups with different steric and electronic properties

Synthesis and Characterization of Air‐Stable Palladium(II) and Copper(I) Ph‐Garphos Complexes and their Applications to Asymmetric Catalysis

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