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

Jin, Fazheng; Zhao, Chenchen; Ma, Hua; Chen, Gong-Jun; Dong, Yu‐Bin

doi:10.1021/acs.inorgchem.9b00963

Cited by 38 publications

(24 citation statements)

References 55 publications

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“…The ligand H 2 L 2 decorated with crown ether groups was achieved from H 2 L 1 by three steps with 52% overall yield. In addition, H 2 L 3 was synthesized as described in previous literature . Full descriptions of the syntheses and characterizations for H 2 L 1 –H 2 L 3 and intermediates are provided in Supporting Information (Figures S1–S11).…”

Section: Resultsmentioning

confidence: 99%

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Artificial Biomolecular Channels: Enantioselective Transmembrane Transport of Amino Acids Mediated by Homochiral Zirconium Metal–Organic Cages

Dong

Gong

et al. 2021

J. Am. Chem. Soc.

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Natural transport channels (or carriers), such as aquaporins, are a distinct type of biomacromolecule capable of highly effective transmembrane transport of water or ions. Such behavior is routine for biology but has proved difficult to achieve in synthetic systems. Perhaps most significantly, the enantioselective transmembrane transport of biomolecules is an especially challenging problem both for chemists and for natural systems. Herein, a group of homochiral zirconium metal−organic cages with four triangular opening windows have been proposed as artificial biomolecular channels for enantioselective transmembrane transport of natural amino acids. These structurally well-defined coordination cages are assembled from six synthetically accessible BINOL-derived chiral ligands as spacers and four n-Bu 3 -Cp 3 Zr 3 clusters as vertices, forming tetrahedral-shaped architectures that feature an intrinsically chiral cavity decorated with an array of specifically positioned binding sites mediated from phenol to phenyl ether to crown ether groups. Fascinatingly, the transformation of single-molecule chirality to global supramolecular chirality within the space-restricted chiral microenvironments accompanies unprecedented chiral amplification, leading to the enantiospecific recognition of amino acids. By virtue of the highly structural stability and excellent biocompatibility, the orientation-independent cages can be molecularly embedded into lipid membranes, biomimetically serving as single-molecular chiral channels for polar-residue amino acids, with the properties that cage-1 featuring hydroxyl groups preferentially transports the L-asparagine, whereas cage-2 attaching crown ether groups spontaneously favor transporting D-arginine. We therefore develop a new type of self-assembled system that can potentially mimic the functions of transmembrane proteins in nature, which is a realistic candidate for further biomedical applications.

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Section: Resultsmentioning

confidence: 99%

“…H 2 L 1 by three steps with 52% overall yield. In addition, H 2 L 3 was synthesized as described in previous literature 60. Full descriptions of the syntheses and characterizations for H 2 L 1 − H…”

mentioning

confidence: 99%

Artificial Biomolecular Channels: Enantioselective Transmembrane Transport of Amino Acids Mediated by Homochiral Zirconium Metal–Organic Cages

Dong

Gong

et al. 2021

J. Am. Chem. Soc.

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“…[ 71–76 ] In other words, this polymer is hydrophilic and dissolves in water when the temperature is below the T c at ≈32 °C, yet it also forms aggregates. [ 77–79 ] Using this unique feature, Karmakar et al ( Figure 5 ) reported that a chromium‐based MOF (MIL‐101) modified by PNIPAM exhibited thermo‐responsive water capture and release behavior. [ 80 ] Forty percent water content could be captured by a MOF at 96% RH and 25 °C.…”

Section: Single Stimulus Mofsmentioning

confidence: 99%

Advances in Functional Metal‐Organic Frameworks Based On‐Demand Drug Delivery Systems for Tumor Therapeutics

Yalamandala

Shen

Min

et al. 2021

Advanced NanoBiomed Research

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Dual on‐demand delivery of therapeutic cargos and energy by transporters can latently mitigate side effects and provide the unique aspects required for precision medicine. To achieve this goal, metal‐organic frameworks (MOFs), hybrid materials constructed from metal ions and polydentate organic linkers, have attracted attention for controlled drug release and energy delivery in tumors. With appropriate characteristics such as tunable pore size, high surface area, and tailorable composition, therapeutic agents (drug molecules or responsive agents) can be effectively encapsulated in MOFs. Based on their intrinsic properties, many physically or chemically responsive agents are able to achieve precise on‐demand drug release and energy generation (thermal or dynamic therapy) using MOFs (as energy absorbers). Herein, the results obtained with various stimuli‐responsive MOFs (including materials from the Institute Lavoisier [MIL], zeolitic imidazolate frameworks [ZIFs], MOFs from the University of Oslo [UiO], and other MOFs) used for tumor suppression are summarized. Furthermore, with the appropriate stimulus, catalytic therapy (caused by the Fenton reaction induced by MOFs) can be provided via the utilization of existing high levels of H2O2 in cancer cells, which potentially elicits immune responses. In addition, the issues impeding clinical translation are also discussed, including the need to overcome tumor heterogeneity and to recognize the innate immune system and possible effects. As the references reveal, additional comprehensive strategies and studies are needed to enable broad applications and potent translational developments.

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“…This is largely due to their robustness and insoluble nature in most of the common organic solvents. The important organic transformations for which CPs have been developed and employed as heterogeneous catalysts include cyanosilylation of aldehydes or ketones [7], Knoevenagel condensation [8], oxidation of alkanes, alcohols or olefins [9], Henry reaction [10,11], ring-opening of epoxides [12], transesterification [13], cascade [14] reactions, etc.…”

Section: Introductionmentioning

confidence: 99%

Pyrene Carboxylate Ligand Based Coordination Polymers for Microwave-Assisted Solvent-Free Cyanosilylation of Aldehydes

et al. 2021

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The new coordination polymers (CPs) [Zn(μ-1κO1:1κO2-L)(H2O)2]n·n(H2O) (1) and [Cd(μ4-1κO1O2:2κN:3,4κO3-L)(H2O)]n·n(H2O) (2) are reported, being prepared by the solvothermal reactions of 5-{(pyren-4-ylmethyl)amino}isophthalic acid (H2L) with Zn(NO3)2.6H2O or Cd(NO3)2.4H2O, respectively. They were synthesized in a basic ethanolic medium or a DMF:H2O mixture, respectively. These compounds were characterized by single-crystal X-ray diffraction, FTIR spectroscopy, thermogravimetric and elemental analysis. The single-crystal X-ray diffraction analysis revealed that compound 1 is a one dimensional linear coordination polymer, whereas 2 presents a two dimensional network. In both compounds, the coordinating ligand (L2−) is twisted due to the rotation of the pyrene ring around the CH2-NH bond. In compound 1, the Zn(II) metal ion has a tetrahedral geometry, whereas, in 2, the dinuclear [Cd2(COO)2] moiety acts as a secondary building unit and the Cd(II) ion possesses a distorted octahedral geometry. Recently, several CPs have been explored for the cyanosilylation reaction under conventional conditions, but microwave-assisted cyanosilylation of aldehydes catalyzed by CPs has not yet been well studied. Thus, we have tested the solvent-free microwave-assisted cyanosilylation reactions of different aldehydes, with trimethylsilyl cyanide, using our synthesized compounds, which behave as highly active heterogeneous catalysts. The coordination polymer 1 is more effective than 2, conceivably due to the higher Lewis acidity of the Zn(II) than the Cd(II) center and to a higher accessibility of the metal centers in the former framework. We have also checked the heterogeneity and recyclability of these coordination polymers, showing that they remain active at least after four recyclings.

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

Cited by 38 publications

References 55 publications

Artificial Biomolecular Channels: Enantioselective Transmembrane Transport of Amino Acids Mediated by Homochiral Zirconium Metal–Organic Cages

Artificial Biomolecular Channels: Enantioselective Transmembrane Transport of Amino Acids Mediated by Homochiral Zirconium Metal–Organic Cages

Advances in Functional Metal‐Organic Frameworks Based On‐Demand Drug Delivery Systems for Tumor Therapeutics

Pyrene Carboxylate Ligand Based Coordination Polymers for Microwave-Assisted Solvent-Free Cyanosilylation of Aldehydes

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