Browse
Submit Data
Databases
API
Help

Dataset Information

26 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Direct and Efficient C(sp3)-H Functionalization of N-Acyl/Sulfonyl Tetrahydroisoquinolines (THIQs) With Electron-Rich Nucleophiles via 2,3-Dichloro-5,6-Dicyano-1,4-Benzoquinone (DDQ) Oxidation.

ABSTRACT: A highly efficient metal-free oxidative direct C(sp3)-H functionalization of N-acyl/sulfonyl 1,2,3,4-tetrahydroisoquinolines (THIQs) with a wide range of electron-rich nucleophiles was accomplished under mild conditions through oxidation with DDQ and subsequent trapping of the resulting reactive and stable N-acyl/sulfonyl iminium ions. The synthetic utility of this method was illustrated by a concise and efficient total synthesis of (±)-benzo[a]quinolizidine (10) in 3 steps from the known N-Cbz 1,2,3,4-THIQ 4b.

SUBMITTER: Yu H

PROVIDER: S-EPMC7403605 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Direct and Efficient C(sp3)-H Functionalization of N-Acyl/Sulfonyl Tetrahydroisoquinolines (THIQs) With Electron-Rich Nucleophiles via 2,3-Dichloro-5,6-Dicyano-1,4-Benzoquinone (DDQ) Oxidation.

Yu Heesun H Kim Hyoungsu H Baek Seung-Hoon SH Lee Dongjoo D

Frontiers in chemistry 20200729

A highly efficient metal-free oxidative direct C(sp3)-H functionalization of N-acyl/sulfonyl 1,2,3,4-tetrahydroisoquinolines (THIQs) with a wide range of electron-rich nucleophiles was accomplished under mild conditions through oxidation with DDQ and subsequent trapping of the resulting reactive and stable N-acyl/sulfonyl iminium ions. The synthetic utility of this method was illustrated by a concise and efficient total synthesis of (±)-benzo[a]quinolizidine (1 ...[more]

PMID: 32850649

Similar Datasets

Mild Method for 2-Naphthylmethyl Ether Protecting Group Removal Using a Combination of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and β-Pinene.

Project description:The use of a combination of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and β-pinene permits the removal of 2-naphthylmethyl (Nap) ether protecting groups on highly sensitive substrates. The reaction tolerates both acid and base sensitive protecting groups, and products are afforded in 68-96% yield. The utility of the method is demonstrated by the removal of the Nap protecting groups on highly sensitive 2,6-dideoxy-sugar disaccharides.

| S-EPMC5387675 | biostudies-literature

2,3-Dichloro-5,6-dicyano-1,4-benzoquinone-catalyzed reactions employing MnO2 as a stoichiometric oxidant.

Project description:Several oxidative reactions can be effected with MnO(2) in the presence of substoichiometric quantities of DDQ. These transformations include oxidative cyclization, deprotection, and dehydrogenation reactions. The use of MnO(2) as a terminal oxidant for DDQ-mediated reactions is attractive based on economical and environmental factors.

| S-EPMC2952688 | biostudies-literature

Thermodynamic and Computational (DFT) Study of Non-Covalent Interaction Mechanisms of Charge Transfer Complex of Linagliptin with 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and Chloranilic acid (CHA).

Project description:This study describes the non-covalent interactions of the charge transfer complex (CT), which was responsible for the synthesis of Linagliptin (LNG) with 2,3-Dichloro-5,6-Dicyano-1,4-benzoquinone (DDQ), or with Chloranilic acid (CHA) complexes in acetonitrile (MeCN) at temperatures of (25 ± 2 °C). Then, a UV-Vis spectrophotometer was utilized to identify Linagliptin (LNG) from these complexes. For the quantitative measurement of Linagliptin in bulk form, UV-Vis techniques have been developed and validated in accordance with ICH criteria for several aspects, including selectivity, linearity, accuracy, precision, LOD, LOQ, and robustness. The optimization of the complex synthesis was based on solvent polarization; the ratio of molecules in complexes; the association constant; and Gibbs energy (ΔG°). The experimental work is supported by the computational investigation of the complexes utilizing density functional theory as well as (QTAIM); (NCI) index; and (RDG). According to the optimized conditions, Beer's law was observed between 2.5-100 and 5-100 µM with correlation coefficients of 1.9997 and 1.9998 for LGN-DDQ and LGN-CHA complexes, respectively. For LGN-DDQ and LGN-CHA complexes, the LOD and LOQ were (1.0844 and 1.4406 μM) and (3.2861 and 4.3655 μM), respectively. The approach was successfully used to measure LGN in its bulk form with high precision and accuracy.

| S-EPMC9572772 | biostudies-literature

Selective oxidation of benzylic and allylic alcohols using Mn(OAc)3/catalytic 2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

Project description:A practical, chemoselective oxidation of alcohols employing catalytic quantities of DDQ as the oxidant and Mn(OAc)(3) as the co-oxidant is described. Electron-rich benzylic alcohols are oxidized efficiently to their corresponding carbonyls, but less electron-rich benzylic alcohols remain unchanged. Allylic alcohols are rapidly oxidized to their corresponding aldehyde or ketone counterparts in high yields. This protocol is operationally simple, employs an inexpensive source of Mn(OAc)(3), has short reaction times, and exhibits a significant chemoselectivity favoring allylic alcohols over benzylic alcohols. This procedure also avoids the use of very large excesses of reagents and sometimes poor reproducibility that characterize previously developed reagents such as MnO(2).

| S-EPMC4482348 | biostudies-literature

Charge Transfer Complexes of Ketotifen with 2,3-Dichloro-5,6-dicyano-p-benzoquinone and 7,7,8,8-Tetracyanoquodimethane: Spectroscopic Characterization Studies.

Project description:The reactions of ketotifen fumarate (KT) with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) as π acceptors to form charge transfer (CT) complexes were evaluated in this study. Experimental and theoretical approaches, including density function theory (DFT), were used to obtain the comprehensive, reliable, and accurate structure elucidation of the developed CT complexes. The CT complexes (KT-DDQ and KT-TCNQ) were monitored at 485 and 843 nm, respectively, and the calibration curve ranged from 10 to 100 ppm for KT-DDQ and 2.5 to 40 ppm for KT-TCNQ. The spectrophotometric methods were validated for the determination of KT, and the stability of the CT complexes was assessed by studying the corresponding spectroscopic physical parameters. The molar ratio of KT:DDQ and KT:TCNQ was estimated at 1:1 using Job's method, which was compatible with the results obtained using the Benesi-Hildebrand equation. Using these complexes, the quantitative determination of KT in its dosage form was successful.

| S-EPMC8038309 | biostudies-literature

DDQ-Promoted Mild and Efficient Metal-Free Oxidative ?-Cyanation of N-Acyl/Sulfonyl 1,2,3,4-Tetrahydroisoquinolines.

Project description:A mild and highly efficient metal-free oxidative ?-cyanation of N-acyl/sulfonyl 1,2,3,4-tetrahydroisoquinolines (THIQs) has been accomplished at an ambient temperature via DDQ oxidation and subsequent trapping of N-acyl/sulfonyl iminium ions with (n-Bu)?SnCN. Employing readily removable N-acyl/sulfonyl groups as protecting groups rather than N-aryl ones enables a wide range of applications in natural product synthesis. The synthetic utility of the method was illustrated using a short and efficient formal total synthesis of (±)-calycotomine in three steps.

| S-EPMC6321290 | biostudies-literature

Surprising unreactivity of cholesterol-5,6-epoxides towards nucleophiles.

Project description:We recently established that drugs used for the treatment and the prophylaxis of breast cancers, such as tamoxifen, were potent inhibitors of cholesterol-5,6-epoxide hydrolase (ChEH), which led to the accumulation of 5,6?-epoxy-cholesterol (5,6?-EC) and 5,6?-epoxy-cholesterol (5,6?-EC). This could be considered a paradox because epoxides are known as alkylating agents with putative carcinogenic properties. We report here that, as opposed to the carcinogen styrene-oxide, neither of the ECs reacted spontaneously with nucleophiles. Under catalytic conditions, 5,6?-EC remains unreactive whereas 5,6?-EC gives cholestan-3?,5?-diol-6?-substituted compounds. These data showed that 5,6-ECs are stable epoxides and unreactive toward nucleophiles in the absence of a catalyst, which contrasts with the well-known reactivity of aromatic and aliphatic epoxides. These data rule out 5,6-EC acting as spontaneous alkylating agents. In addition, these data support the existence of a stereoselective metabolism of 5,6?-EC.

| S-EPMC3307648 | biostudies-literature

Charge Transfer Complex between O-Phenylenediamine and 2, 3-Dichloro-5, 6-Dicyano-1, 4-Benzoquinone: Synthesis, Spectrophotometric, Characterization, Computational Analysis, and its Biological Applications.

Project description:UV-vis electronic absorption spectroscopy was used to investigate the new molecular charge transfer complex (CTC) interaction between electron donor O-phenylenediamine (OPD) and electron acceptor 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ). The CTC solution state analysis was carried out by two different polarities. The stoichiometry of the prepared CTC was determined by using Job's, photometric, and conductometric titration methods and was detemined to be 1:1 in both solvents (at 298 K). The formation constant and molar extinction coefficient were determined by applying the modified (1:1) Benesi-Hildebrand equation. The thermodynamic parameter ΔG° result indicated that the charge transfer reaction was spontaneous.The stability of the synthesized CTC was evaluated by using different spectroscopic parameters like the energy, ionization potential, oscillator strength, resonance energy, dissociation energy, and transition dipole moment. The synthesized solid CTC was characterized by using different analytical methods, including elemental analysis, Fourier transform infrared, nuclear magnetic resonance, TGA-DTA, and powder X-ray diffraction. The biological evolution of the charge transfer (CT) complex was studied by using DNA binding and antibacterial analysis. The CT complex binding with calf thymus DNA through an intercalative mode was observed from UV-vis spectral study. The CT complex produced a good binding constant value (6.0 × 105 L.mol-1). The antibacterial activity of the CT complex shows notable activity compared to the standard drug, tetracycline. These results reveal that the CT complex may in future be used as a bioactive drug. The hypothetical DFT estimations of the CT complex supported the experimental studies.

| S-EPMC9118382 | biostudies-literature

Palladium-catalyzed direct C-H functionalization of benzoquinone.

Project description:A direct Pd-catalyzed C-H functionalization of benzoquinone (BQ) can be controlled to give either mono- or disubstituted BQ, including the installation of two different groups in a one-pot procedure. BQ can now be directly functionalized with aryl, heteroaryl, cycloalkyl, and cycloalkene groups and, moreover, the reaction is conducted in environmentally benign water or acetone as solvents.

| S-EPMC4502976 | biostudies-literature

2,2-Dichloro-N-(4-methyl-phenyl-sulfonyl)acetamide.

Project description:The N-H and C=O bonds in the title compound, C(9)H(9)Cl(2)NO(3)S, are trans to each other, similar to what is observed in 2,2,2-trimethyl-N-(phenyl-sulfon-yl)acetamide and 2,2,2-trimethyl-N-(4-methyl-phenyl-sulfon-yl)acetamide. The bond parameters in the title compound are also similar to those in the aforementioned two structures. N-H⋯O hydrogen bonds connect the mol-ecules into chains running along the a axis.

| S-EPMC2962122 | biostudies-literature