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Yakugaku Zasshi : Journal of the... Jul 2010A copper-catalyzed synthesis of 2-(aminomethyl)indole through domino three-component coupling-cyclization has been developed. This reaction proceeds through Mannich-type... (Review)
Review
A copper-catalyzed synthesis of 2-(aminomethyl)indole through domino three-component coupling-cyclization has been developed. This reaction proceeds through Mannich-type coupling of 2-ethynylanilines, aldehydes, and secondary amines, followed by hydroamination. This indole formation was applicable to the synthesis of 4-methylene-2,3,4,9-tetrahyro-1H-pyrido[3,4-b]indoles and 5,6,7,8-tetrahydrobenzo[e]indolo[2,3-c]azepines via palladium-catalyzed C-H functionalization at the 3-position of indole. A combination of the three-component indole formation with nucleophilic cyclization promoted by t-BuOK or MsOH provides an effective access to beta-carboline scaffolds. Indole-fused 1,4-diazepines were also synthesized through deprotection/N-arylation at the nitrogen atom of indole by one-pot addition of MeONa after the formation of 2-(aminomethyl)indoles. In relation to the three-component indole formation, a novel four-component synthesis of isoquinolines has been developed. This isoquinoline formation includes Mannich-type reaction of 2-ethynylbenzaldehyde with (HCHO)(n) and secondary amine, imine formation with t-BuNH(2), isoquinoline formation, and elimination of t-butyl group to directly afford 3-(aminomethyl)isoquinolines in good yields. By the use of an alkane diamine instead of t-BuNH(2), fused 3-(aminomethyl)isoquinoline derivatives were obtained by cascade cyclization and oxidation.
Topics: Alkanes; Catalysis; Copper; Cyclization; Diamines; Drug Design; Indoles; Isoquinolines; Nitrogen; Oxidation-Reduction
PubMed: 20606372
DOI: 10.1248/yakushi.130.925 -
The Journal of Organic Chemistry Jun 2023Chiral Ni complexes have revolutionized both asymmetric acid-base and redox catalysis. However, the coordination isomerism of Ni complexes and their open-shell property...
Chiral Ni complexes have revolutionized both asymmetric acid-base and redox catalysis. However, the coordination isomerism of Ni complexes and their open-shell property still often hinder the elucidation of the origin of their observed stereoselectivity. Here, we report our experimental and computational investigations to clarify the mechanism of β-nitrostyrene facial selectivity switching in Ni(II)-diamine-(OAc)-catalyzed asymmetric Michael reactions. In the reaction with a dimethyl malonate, the Evans transition state (TS), in which the enolate binds in the same plane with the diamine ligand, is identified as the lowest-energy TS to promote C-C bond formation from the face in β-nitrostyrene. In contrast, a detailed survey of the multiple potential pathways in the reaction with α-keto esters points to a clear preference for our proposed C-C bond-forming TS, in which the enolate coordinates to the Ni(II) center in apical-equatorial positions relative to the diamine ligand, thereby promoting face addition in β-nitrostyrene. The N-H group plays a key orientational role in minimizing steric repulsion.
Topics: Nickel; Diamines; Ligands; Carboxylic Acids; Catalysis
PubMed: 36813263
DOI: 10.1021/acs.joc.2c02732 -
Biomacromolecules Jan 2023The reductive amination of dialdehyde cellulose (DAC) with 2-picoline borane was investigated for its applicability in the generation of bioderived thermoplastics. Five...
The reductive amination of dialdehyde cellulose (DAC) with 2-picoline borane was investigated for its applicability in the generation of bioderived thermoplastics. Five primary amines, both aliphatic and aromatic, were introduced to the cellulose backbone. The influences of the side chains on the course of the reaction were examined by various analytical techniques with microcrystalline cellulose as a model compound. The obtained insights were transferred to a 39%-oxidized softwood kraft pulp to study the thermal properties of thereby generated high-molecular-weight thermoplastics. The number-average molecular weights () of the diamine celluloses, ranging from 60 to 82 kD, were investigated by gel permeation chromatography. The diamine celluloses exhibited glass transition temperatures () from 71 to 112 °C and were stable at high temperatures. Diamine cellulose generated from aniline and DAC showed the highest conversion, the highest (112 °C), and a narrow molecular weight distribution ( of 1.30).
Topics: Amination; Amines; Cellulose; Diamines
PubMed: 36542819
DOI: 10.1021/acs.biomac.2c01022 -
Molecules (Basel, Switzerland) Oct 2022Diisocyanates are highly reactive compounds with two functional isocyanate groups. The exposure of diisocyanates is associated with severely adverse health effects, such...
Diisocyanates are highly reactive compounds with two functional isocyanate groups. The exposure of diisocyanates is associated with severely adverse health effects, such as asthma, inflammation in the respiratory tract, and cancer. The hydrolysis product from diisocyanates to related diamines is also a potential carcinogen. Here, we developed an effective, accurate, and precise method for simultaneous determination of residual diisocyanates and related diamines in biodegradable mulch films, based on N-ethoxycarbonylation derivatization and gas chromatography-mass spectrometry. The method development included the optimization of ultrasonic hydrolysis and extraction, screening of N-ethoxycarbonylation conditions with ethyl chloroformate, evaluation of the diamines degradation, and analysis of the fragmentation mechanisms. Under the optimum experimental conditions, good linearity was observed with R2 > 0.999. The extraction recoveries were found in the range of 93.9−101.2% with repeatabilities and reproducibilities in 0.89−8.12% and 2.12−10.56%, respectively. The limits of detection ranged from 0.0025 to 0.057 µg/mL. The developed method was applied to commercial polybutylene adipate co-terephthalate (PBAT) biodegradable mulch film samples for analysis of the diverse residual diisocyanates and related diamine additives. The components varied greatly among the sample from different origin. Overall, this study provides a reliable method for assessing safety in biodegradable mulch films.
Topics: Carcinogens; Diamines; Gas Chromatography-Mass Spectrometry; Isocyanates
PubMed: 36235287
DOI: 10.3390/molecules27196754 -
International Journal of Nanomedicine 2014Near-infrared dyes can be used as theranostic agents in cancer management, based on their optical imaging and localized hyperthermia capabilities. However, their...
Near-infrared dyes can be used as theranostic agents in cancer management, based on their optical imaging and localized hyperthermia capabilities. However, their clinical translatability is limited by issues such as photobleaching, short circulation times, and nonspecific biodistribution. Nanoconjugate formulations of cyanine dyes, such as IR820, may be able to overcome some of these limitations. We covalently conjugated IR820 with 6 kDa polyethylene glycol (PEG)-diamine to create a nanoconjugate (IRPDcov) with potential for in vivo applications. The conjugation process resulted in nearly spherical, uniformly distributed nanoparticles of approximately 150 nm diameter and zeta potential -0.4±0.3 mV. The IRPDcov formulation retained the ability to fluoresce and to cause hyperthermia-mediated cell-growth inhibition, with enhanced internalization and significantly enhanced cytotoxic hyperthermia effects in cancer cells compared with free dye. Additionally, IRPDcov demonstrated a significantly longer (P<0.05) plasma half-life, elimination half-life, and area under the curve (AUC) value compared with IR820, indicating larger overall exposure to the theranostic agent in mice. The IRPDcov conjugate had different organ localization than did free IR820, with potential reduced accumulation in the kidneys and significantly lower (P<0.05) accumulation in the lungs. Some potential advantages of IR820-PEG-diamine nanoconjugates may include passive targeting of tumor tissue through the enhanced permeability and retention effect, prolonged circulation times resulting in increased windows for combined diagnosis and therapy, and further opportunities for functionalization, targeting, and customization. The conjugation of PEG-diamine with a near-infrared dye provides a multifunctional delivery vector whose localization can be monitored with noninvasive techniques and that may also serve for guided hyperthermia cancer treatments.
Topics: Algorithms; Animals; Antineoplastic Agents; Cell Line, Tumor; Cell Proliferation; Diamines; Humans; Hyperthermia, Induced; Indocyanine Green; Mice; Nanoconjugates; Nanotechnology; Optical Imaging; Polyethylene Glycols; Surgery, Computer-Assisted; Tissue Distribution
PubMed: 25336944
DOI: 10.2147/IJN.S69550 -
The Journal of Biological Chemistry Jan 1954
Topics: Amine Oxidase (Copper-Containing); Amines; Cadaverine
PubMed: 13130568
DOI: No ID Found -
Molecules (Basel, Switzerland) Oct 2022This paper presents the data of research studies on the mechanisms, kinetics and thermodynamics of decomposition of three high-energy compounds:...
This paper presents the data of research studies on the mechanisms, kinetics and thermodynamics of decomposition of three high-energy compounds: [1,2,4]triazolo[4,3-][1,2,4,5]tetrazine-3,6-diamine (TTDA), 3-amino-6-hydrazino[1,2,4]triazolo[4,3-][1,2,4,5]tetrazine (TTGA) and 3,6-dinitroamino[1,2,4]triazolo[4,3-][1,2,4,5]tetrazine (DNTT). The points of change of the reaction mechanisms under thermal effects with different intensities from 0.1 to 2000 s have been established. The values of activation and induction energies for the limiting stages of decomposition have been obtained. The formation of nanostructured carbon nitride (α-CN) in condensed decomposition products, cyanogen (CN) and hydrogen cyanide (HCN) in gaseous products have been shown. Concentration-energy diagrams for the reaction products have been compiled. The parameters of heat resistance and thermal safety proved to be: 349.5 °C and 358.2 °C for TTDA; 190.3 °C and 198.0 °C for TTGA; 113.4 °C and 114.1 °C for DNTT. The energy and thermodynamic properties have also been estimated. This work found the activation energy of the decomposition process to be 129.0 kJ/mol for TTDA, 212.2 kJ/mol for TTGA and 292.2 kJ/mol for DNTT. The average induction energy of the catalytic process (Ecat) for TTGA was established to be 21 kJ/mol, and for DNTT-1500-1700 kJ/mol. The induction energy of the inhibition process (Eing) of TTDA was estimated to be 800-1400 kJ/mol.
Topics: Hydrogen Cyanide; Thermodynamics; Kinetics; Hot Temperature; Heterocyclic Compounds; Diamines
PubMed: 36296568
DOI: 10.3390/molecules27206966 -
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 -
The Journal of Organic Chemistry Nov 2022A highly efficient enantioselective α-nitrogenation method of α,α-disubstituted aldehydes with azodicarboxylates promoted by a chiral carbamate-monoprotected...
A highly efficient enantioselective α-nitrogenation method of α,α-disubstituted aldehydes with azodicarboxylates promoted by a chiral carbamate-monoprotected cyclohexa-1,2-diamine as organocatalyst has been developed. The process was carried out without any solvent, and the corresponding α,α-disubstituted α-nitrogenated aldehydes were obtained with excellent yields and enantioselectivities up to 99% . The sustainability of the procedure was established through the calculation of green metrics, such as EcoScale and E-factor. In addition, theoretical calculations have been used to justify the obtained enantioselectivity sense.
Topics: Aldehydes; Stereoisomerism; Solvents; Catalysis; Diamines
PubMed: 36283071
DOI: 10.1021/acs.joc.2c01919 -
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