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Organic Letters Feb 2021A decarboxylative cross-coupling reaction of α-amino acids with nitrones via visible-light-induced photoredox catalysis has been established for easy access to β-amino...
A decarboxylative cross-coupling reaction of α-amino acids with nitrones via visible-light-induced photoredox catalysis has been established for easy access to β-amino hydroxylamines and vicinal diamines with structural diversity, which is featured with simple operation, mild conditions, readily available α-amino acids, and a broad scope of nitrone substrates. The application of this protocol can furnish efficient synthetic strategies for some valuable vicinal diamine-containing molecules.
Topics: Amino Acids; Catalysis; Diamines; Light; Molecular Structure; Nitrogen Oxides; Photochemical Processes
PubMed: 33433222
DOI: 10.1021/acs.orglett.0c04101 -
The Journal of Organic Chemistry Sep 2021Although dynamic reactions of imines have been extensively studied, the dynamic behaviors manipulated by chirality remain nearly unexplored. In this work,...
Although dynamic reactions of imines have been extensively studied, the dynamic behaviors manipulated by chirality remain nearly unexplored. In this work, enantioselective amine exchange reactions were demonstrated as a first example via the reaction of enantiomeric chiral amines such as natural amino acids with a series of innovative axially chiral 1,1'-binaphthyl-2,2'-diamine (BNDA)-based imines that were prepared from the condensation reactions between BNDA and salicylaldehyde (SA) or its derivatives. This enantioselective dynamic behavior can be directly indicated by the degree of the fluorescence response of the -configuration of imines to the d-enantiomer of chiral amine, because the released BNDA can serve as the fluorescence signal output when the amine exchange reaction occurs, which is far higher than the response to its l-enantiomer under identical experimental conditions. For the -configuration of chiral imines, the fluorescence response is the opposite. The enantioselective exchange reaction can be tuned by altering the electron-withdrawing or electron-donating capability of the substituent at position 4 or 5 of the SA part of chiral imines. Not only -OH groups in SA-based imines but also protic solvents used as reaction media were found to be important to the dynamic behavior at high rates.
Topics: Amines; Catalysis; Diamines; Imines; Stereoisomerism
PubMed: 34482692
DOI: 10.1021/acs.joc.1c01620 -
Ultrasonics Sonochemistry Apr 2019Under mode of ultrasonic vibration, the neutral octahedral mononuclear [trans-CuBr(N ∩ N)]·3HO complex with N ∩ N = 2,2-dimethylpropane-1,3-diamine was... (Review)
Review
Under mode of ultrasonic vibration, the neutral octahedral mononuclear [trans-CuBr(N ∩ N)]·3HO complex with N ∩ N = 2,2-dimethylpropane-1,3-diamine was obtained. The structure of the desired complex was characterized by UV-Vis. spectroscopy, FT-IR, EDX, MS, SEM, TG/DTA and CHN-analysis. The octahedral-structure of the desired Cu(II) complex was proven via XRD single-crystal diffraction and its molecular interactions were computed by Hirschfeld surface analysis. Alcohol (as solvent) and short ultrasonic vibration dose period played a critical role in sonochemistry synthesis of octahedral neutral trans-CuBr(N ∩ N) complex instead of trigonal bi-pyramidal monocation [CuBr(N ∩ N)]Br one. Due to the Jahn-Teller effect, the complex exhibited a trans bonds elongation along Br-Cu-Br axis originating a distorted-octahedral Cu(II), as revealed by the XRD measurements (Br-Cu = 3.04 Å). Therefore, the Solvatochromic behavior of the complex was successfully performed since the trans di-bromide ions are loosely coordinated to Cu(II) center, the change in complex solutions colors by using different solvents which can be detected even by naked-eye supported atypical Jahn-Teller elongation effect formation. TG/DTA and Flynn Wall Ozawa (FWO) isoconversional kinetic methods were applied for the complex to figure out the thermal behavior, kinetic of the ligands de-structured and estimate its Ea/α relation. The complex binding mode to the CT-DNA was examined by UV-vis. spectroscopic, melting curve, CV and viscosity tests. The complex exhibited very strong DNA binding via an intercalation mode of coordination with K = 6.5 × 10 value.
Topics: Animals; Cattle; Chemistry Techniques, Synthetic; Coordination Complexes; Copper; Crystallography, X-Ray; DNA; Diamines; Electrochemistry; Kinetics; Ligands; Models, Molecular; Molecular Conformation; Solvents; Stereoisomerism; Ultrasonic Waves
PubMed: 30573435
DOI: 10.1016/j.ultsonch.2018.12.019 -
European Journal of Medicinal Chemistry Feb 2020FGF2-FGFR1 autocrine pathway activation reduces the sensitivity of non-small cell lung cancer (NSCLC) cells to EGFR inhibitors like Gefitinib. Therefore, dual-specific...
FGF2-FGFR1 autocrine pathway activation reduces the sensitivity of non-small cell lung cancer (NSCLC) cells to EGFR inhibitors like Gefitinib. Therefore, dual-specific drugs targeting EGFR and FGFR with high selectivity and activity are required. Through structure analysis of excellent EGFR inhibitors and FGFR inhibitors, we designed and synthesized 33 4,6-pyrimidinediamine derivatives as dual EGFR and FGFR inhibitors and selected BZF 2 as a potential EGFR and FGFR inhibitor after initial cell screening. Then, through kinase testing and western blot analysis, BZF 2 was defined as a dual EGFR and FGFR inhibitor with high selectivity and activity. Biological evaluation of NSCLC cell lines with the FGF2-FGFR1 autocrine loop indicated that BZF 2 significantly inhibited cell proliferation (IC values for H226 and HCC827 GR were 2.11 μM, and 0.93 μM, respectively), cell migration, and induced cell apoptosis and cell cycle arrest. Anti-tumor activity test in vivo showed that BZF 2 obviously shrank tumor size. Therefore, BZF 2 is a highly selective and potent dual EGFR/FGFR compound with promising therapeutic effects against EGFR/FGFR1-positive NSCLC.
Topics: Antineoplastic Agents; Carcinoma, Non-Small-Cell Lung; Diamines; Dose-Response Relationship, Drug; Drug Discovery; Drug Screening Assays, Antitumor; ErbB Receptors; Humans; Lung Neoplasms; Models, Molecular; Molecular Structure; Protein Kinase Inhibitors; Pyrimidines; Receptor, Fibroblast Growth Factor, Type 1; Structure-Activity Relationship
PubMed: 31846829
DOI: 10.1016/j.ejmech.2019.111943 -
Bioorganic & Medicinal Chemistry Apr 2019Janus kinases (JAKs) play a key role in the proliferation, apoptosis and differentiation of immune cells, and JAKs are considered as an attractive target for the...
Janus kinases (JAKs) play a key role in the proliferation, apoptosis and differentiation of immune cells, and JAKs are considered as an attractive target for the treatment of inflammatory and autoimmune diseases. Here we show the design and optimization of pyrimidine-4,6-diamine derivatives as selectivity JAK3 inhibitors. Compound 11e, which might interact with unique cysteine (Cys909) residue in JAK3, exhibited excellent JAK3 inhibitory activity (IC = 2.1 nM) and high JAK kinase selectivity. In cellular assay, 11e showed moderate potency inhibiting IL-2-stimulated T cell proliferation. The data supports the further development of novel JAKs inhibitors.
Topics: Animals; Binding Sites; Cell Proliferation; Diamines; Drug Design; Humans; Janus Kinase 1; Janus Kinase 2; Janus Kinase 3; Molecular Docking Simulation; Protein Kinase Inhibitors; Protein Structure, Tertiary; Pyrimidines; Rats; Structure-Activity Relationship; T-Lymphocytes
PubMed: 30853331
DOI: 10.1016/j.bmc.2019.03.009 -
Journal of the American Chemical Society Jul 2022The 1,2-diamine motif is prevalent in natural products, small-molecule pharmaceuticals, and catalysts for asymmetric synthesis. Transition metal catalyzed alkene...
The 1,2-diamine motif is prevalent in natural products, small-molecule pharmaceuticals, and catalysts for asymmetric synthesis. Transition metal catalyzed alkene diazidation has evolved to be an attractive strategy to access vicinal primary diamines but remains challenging, especially for practical applications, due to the restriction to a certain type of olefins, the frequent use of chemical oxidants, and the requirement for high loadings of metal catalysts (1 mol % or above). Herein we report a scalable Cu-electrocatalytic alkene diazidation reaction with 0.02 mol % (200 ppm) of copper(II) acetylacetonate as the precatalyst without exogenous ligands. In addition to its use of low catalyst loading, the electrocatalytic method is scalable, compatible with a broad range of functional groups, and applicable to the diazidation of α,β-unsaturated carbonyl compounds and mono-, di-, tri-, and tetrasubstituted unactivated alkenes.
Topics: Alkenes; Catalysis; Copper; Diamines; Ligands
PubMed: 35772000
DOI: 10.1021/jacs.2c05126 -
Journal of Inorganic Biochemistry Nov 2022The electrochemical oxidation of anodic metal copper in a solution of the ligands N-[(5-tert-butyl-2-hydroxyphenyl)methylidine]-N'-tosylbenzene-1,2-diamine [HL] and...
The electrochemical oxidation of anodic metal copper in a solution of the ligands N-[(5-tert-butyl-2-hydroxyphenyl)methylidine]-N'-tosylbenzene-1,2-diamine [HL] and N-[(3,5-di-tert-butyl-2-hydroxyphenyl)methylidine]-N'-tosylbenzene-1,2-diamine, [HL] afforded homoleptic [CuL] compounds or solvate [CuLS] complexes. The addition to the electrochemical cell of coligands (L') such as 2,2'-bipyridine (2-bpy), 4,4'-bipyridine(4-bpy) or 1,10-phenanthroline (phen) allowed the synthesis, in one step, of heteroleptic [CuLL'] compounds, namely [CuL(HO)] (1), [CuL(2,2'-bpy)]⋅CHCN (2), [CuL(phen)]·HO (3), [CuL(4,4'-bpy)] (4), [CuL(CHOH)] (5), [CuL(2,2'-bpy)] (6), [CuL(phen)] (7) and [CuL(4,4'-bpy)] (8). The crystal structures of both ligands, HL, HL, and those of the complexes (2), (4), (5), (6) and (7) have been determined by X-ray diffraction techniques. Coordination polyhedron around metal atom is square planar for [CuL(CHOH)] (5) and [CuL(4,4'-bpy)] (4) and square pyramid for the other complexes with additional chelating ligands. The cytotoxic activity of this new series of copper(II) complexes against the SH-SY5Y neuroblastoma cell line and U87-MG and U373-MG glioblastoma cell lines has been investigated. Most of the test compounds showed higher activity than cisplatin in the three cell lines. Among this series, compound [CuL(phen)] (3) displayed the highest activity with IC equal to 1.77 μM on SH-SY5Y whereas compound [CuL(4.4'-bpy)] (4) resulted the most potent compounds on U87 MG and U373 MG glioblastoma cell lines. Studies on the cytotoxic activity of these derivatives suggest that these compounds induce cell death by a mechanism other than apoptosis.
Topics: 2,2'-Dipyridyl; Antineoplastic Agents; Cisplatin; Coordination Complexes; Copper; Crystallography, X-Ray; Diamines; Glioblastoma; Humans; Ligands; Neuroblastoma; Phenanthrolines; Schiff Bases
PubMed: 36055108
DOI: 10.1016/j.jinorgbio.2022.111975 -
Journal of the American Chemical Society Nov 2022Diamine-appended Mg(dobpdc) (dobpdc = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) metal-organic frameworks are a promising class of CO adsorbents, although their stability...
Diamine-appended Mg(dobpdc) (dobpdc = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) metal-organic frameworks are a promising class of CO adsorbents, although their stability to SO─a trace component of industrially relevant exhaust streams─remains largely untested. Here, we investigate the impact of SO on the stability and CO capture performance of dmpn-Mg(dobpdc) (dmpn = 2,2-dimethyl-1,3-propanediamine), a candidate material for carbon capture from coal flue gas. Using SO breakthrough experiments and CO isobar measurements, we find that the material retains 91% of its CO capacity after saturation with a wet simulated flue gas containing representative levels of CO and SO, highlighting the robustness of this framework to SO under realistic CO capture conditions. Initial SO cycling experiments suggest dmpn-Mg(dobpdc) may achieve a stable operating capacity in the presence of SO after initial passivation. Evaluation of several other diamine-Mg(dobpdc) variants reveals that those with , (1°,1°) diamines, including dmpn-Mg(dobpdc), are more robust to humid SO than those featuring , (1°,2°) or , (1°,3°) diamines. Based on the solid-state N NMR spectra and density functional theory calculations, we find that under humid conditions, SO reacts with the metal-bound primary amine in 1°,2° and 1°,3° diamine-appended Mg(dobpdc) to form a metal-bound bisulfite species that is charge balanced by a primary ammonium cation, thereby facilitating material degradation. In contrast, humid SO reacts with the free end of 1°,1° diamines to form ammonium bisulfite, leaving the metal-diamine bond intact. This structure-property relationship can be used to guide further optimization of these materials for CO capture applications.
Topics: Sulfur Dioxide; Diamines; Carbon Dioxide; Amines; Carbon
PubMed: 36265017
DOI: 10.1021/jacs.2c07498 -
Journal of Inorganic Biochemistry Sep 2021A family of combined Kojic acid and polyamine derivatives has been synthesized as phosphate anion and metal ion ligands. The stoichiometry, stability and structure of...
A family of combined Kojic acid and polyamine derivatives has been synthesized as phosphate anion and metal ion ligands. The stoichiometry, stability and structure of the ion/ligand adducts were determined by H NMR spectroscopy, potentiometry, EXAFS and DFT calculations. The presented dual ligands bind effectively both phosphate anions and metal ions and could be used as effective ion receptors in challenging water conditions in the broad pH range. A careful analysis of the heatmaps of the stability constants allows to choose the most appropriate ligand for the ion for qualitative and/or quantitative analysis in water, without analyte pre-treatment. Extremely high-water solubility (>0.6 M) and ion(s)/ligand stability of the adducts in the pH 3-11 are the greatest advantages of the presented here molecules over other known ion sensors. The presented here molecules represent an innovative class of dual metal/anion ligands, with perspective of medical and environmental use.
Topics: Chelating Agents; Coordination Complexes; Density Functional Theory; Diamines; Hydrogen-Ion Concentration; Ligands; Metals; Models, Chemical; Phosphates; Pyrones
PubMed: 34171770
DOI: 10.1016/j.jinorgbio.2021.111520 -
Scientific Reports Feb 2018A Schiff base ligand (SBL), N, N-bis (anthracen-9-ylmethylene) pyridine-2, 3-diamine, was synthesized through the condensation of 2,6-diaminopyridine and...
A Schiff base ligand (SBL), N, N-bis (anthracen-9-ylmethylene) pyridine-2, 3-diamine, was synthesized through the condensation of 2,6-diaminopyridine and anthracene-9-carbaldehyde using a 1:2 ratio. H NMR spectra confirmed the observation of non-involvement aromatic carboxylic proton in SBL. A novel series of lanthanide (i.e., praseodymium (Pr), erbium (Er), and ytterbium (Yb))-based SBL metal complexes was successfully synthesized, and their functional groups were elaborately demonstrated using UV-visible, Fourier transform infrared (FT-IR), and fluorescence spectroscopy analyses. FT-IR spectral studies revealed that SBL behaved as a bidentate ligand and it was structured with metal ions by the two azomethine nitrogens. The synthesized SBL-based metal complexes were elaborately performed for cytotoxicity activity versus Vero, human breast cancer (MCF7), and cervical (HeLa) anticancer cell lines.
Topics: Anthracenes; Cell Line, Tumor; Coordination Complexes; Diamines; Electron Spin Resonance Spectroscopy; Humans; Lanthanoid Series Elements; Ligands; Magnetic Resonance Spectroscopy; Microbial Sensitivity Tests; Pyridines; Schiff Bases; Spectrophotometry, Infrared; Spectroscopy, Fourier Transform Infrared
PubMed: 29445233
DOI: 10.1038/s41598-018-21366-1