Direct Transamidation of Thioamides with Amines via Acetophenone-Promoted Enamine Catalysis under Metal-Free Conditions.

Herein, we developed a highly selective, efficient, and simple method for direct transamidation of thioamides with amines, promoted by commercially available acetophenone under metal-/solvent-free conditions. The reaction tolerated a wide range of functional groups and substrates, including single- or double-thioamides, benzylamines, or alkyl/cycloalkyl-substituted aliphatic amines. The present protocol can be applied to gram-scale in good yields. In addition, the Pt-/Ni-complexes of double-transamidation products were obtained in good to excellent yields. The investigation of photophysical properties indicated that the fluorescence spectra of Pt-complexes showed an emission band centered at 550-750 nm and exhibited red fluorescence when irradiated by a UV lamp (365 nm).

Self-assembly synthesis of diorganotin complexes based on arylformylhydrazone possessing ONO donor set: anticancer activity and mechanism.

Fourteen new organotin(IV) complexes were successfully synthesized and characterized by elemental analyses, Fourier transform infrared spectroscopy (FT-IR), multinuclear (1H, 13C, and 119Sn) NMR spectroscopy, high-resolution mass spectrometry (HRMS), and X-ray single-crystal techniques. Crystallographic data showed that the complexes 1b, 2b, 3b, and 5b were macrocyclic compounds, 4b exhibited a one-dimensional spiral chain structure with distorted trigonal bipyramidal geometry, other complexes were centrosymmetric dimers, and there was an Sn2O2 four-membered ring in the middle of the molecule. In-vitro anticancer activity against the three human tumor cell lines NCI-H460, MCF-7, and HepG2 was studied, and the dibutyltin complex 5a is a more potent antitumor agent than other complexes and cisplatin. Cell apoptosis study of 5a with the highest activity on HepG2 cancer cell lines was done by flow cytometry; it was shown that the antitumor activity of 5a was related to apoptosis, and it inhibited proliferation by blocking cells in the G2/M phase. The single-cell gel electrophoresis assay results show that 5a induces DNA damage. 5a interacts with ct-DNA by intercalating the mode of interaction. UV-visible absorption spectrometry, fluorescence competitive, viscosity measurements, and gel electrophoresis results also support the intercalative mode of interaction for 5a with DNA.

Clinical Application of a 3D-Printed Positioning Module and Navigation Template for Percutaneous Vertebroplasty.

BACKGROUND: This study aimed to evaluate a personalized 3D-printed percutaneous vertebroplasty positioning module and navigation template based on preoperative CT scan data that was designed to treat patients with vertebral compression fractures caused by osteoporosis. METHODS: A total of 22 patients with vertebral compression fractures admitted to our hospital were included in the study. Positioning was performed with the new 3D-printed positioning module, and the navigation template was used for patients in the experimental group, and the traditional perspective method was used for patients in the control group. The experimental group consisted of 11 patients, 2 males and 9 females, with a mean age of 67.27 ± 11.86 years (range: 48 to 80 years), and the control group consisted of 11 patients, 3 males and 8 females, with a mean age of 74.27 ± 7.24 years (range: 63 to 89 years). The puncture positioning duration, number of intraoperative fluoroscopy sessions, and preoperative and postoperative visual analog scale (VAS) scores were statistically analyzed in both groups. RESULTS: The experimental group had shorter puncture positioning durations and fewer intraoperative fluoroscopy sessions than the control group, and the differences were statistically significant (P < .05). There were no significant differences in age or preoperative or postoperative VAS scores between the two groups (P > .05). CONCLUSIONS: The new 3D-printed vertebroplasty positioning module and navigation template shortened the operation time and reduced the number of intraoperative fluoroscopy sessions. It also reduced the difficulty in performing percutaneous vertebroplasty and influenced the learning curve of senior doctors learning this operation to a certain degree.

Brønsted acid-promoted thiazole synthesis under metal-free conditions using sulfur powder as the sulfur source.

A Brønsted acid-promoted sulfuration/annulation reaction for the one-pot synthesis of bis-substituted thiazoles from benzylamines, acetophenones, and sulfur powder has been developed. One C-N bond and multi C-S bonds were selectively formed in one pot. The choice of the Brønsted acid was the key to the high efficiency of this transformation under metal-free conditions.

Iodine-catalyzed convergent aerobic dehydro-aromatization toward benzazoles and benzazines.

An iodine-catalyzed aerobic dehydro-aromatization has been developed, providing straightforward and efficient access to various benzoazoles and benzoazines. The present transition-metal-free protocol enables the dehydro-aromatization of tetrahydrobenzazoles and tetrahydroquinolines with molecular oxygen as the green oxidant, along with some other N-heterocycles. Hence, a broad range of heteroaromatic compounds are generated in moderate to good yields under facile reaction conditions.

A Three-Component Strategy for Benzoselenophene Synthesis under Metal-Free Conditions Using Selenium Powder.

An efficient three-component benzoselenophenes formation has been developed from substituted indoles, acetophenones, and selenium powder under metal-free conditions. 2-Aryl indoles played an important role to promote benzoselenophene formation from acetophenone derivatives and selenium powder. One C-C and two C-Se bonds were selectively formed to provide 40 new benzoselenophenes in good yields.

Metal-Free Double Csp2-H Bond Functionalization: Strategy for Synthesizing Benzo[ a]carbazoles from 2-Arylindoles and Acetophenones/Alkynes.

A metal-free strategy for the synthesis of benzocarbazoles from 2-arylindoles and aryl ketones is developed. Various 2-aryl-3-vinyl-indoles were generated in situ through dehydrative condensation of aryl ketones and indoles. These key intermediates could be selectively converted into the corresponding benzo[ a]carbazoles via a direct cyclization process between two Csp2-H bonds. Furthermore, terminal alkynes also could be used as the versatile C2 source to afford the corresponding products in good yields.

Metal- and base-free synthesis of imidazo[1,2-a]pyridines through elemental sulfur-initiated oxidative annulation of 2-aminopyridines and aldehydes.

The elemental sulfur-promoted oxidative cyclization reaction for the efficient synthesis of substituted imidazo[1,2-a]pyridines has been developed. Easily available 2-aminopyridines and aldehydes were directly assembled in a highly atom-economical fashion through oxidative annulation under metal- and base-free conditions. Besides arylacetaldehydes, aliphatic aldehydes were also compatible with this system to deliver the alkyl-substituted imidazo[1,2-a]pyridines in excellent yields with the capability of gram-scale synthesis.

One-Pot Cascade Synthesis of Substituted Carbazoles from Indoles, Ketones, and Alkenes Using Oxygen as the Oxidant.

An efficient one-pot two-step indole-to-carbazole strategy has been developed. This transition metal-free methodology uses oxygen as the sole oxidant and starts from cheap and readily available indoles, ketones, and alkenes. The present protocol efficiently enables the assembly of a diverse array of substituted carbazole products with good regioselectivity and broad tolerance of functional groups.

Indole-to-Carbazole Strategy for the Synthesis of Substituted Carbazoles under Metal-Free Conditions.

An efficient indole-to-carbazole strategy has been developed under metal-free conditions. This carbazole formation was highly promoted by NH4I with high regioselectivity through formal [2 + 2 + 2] annulation of indoles, ketones, and nitroolefins. It thus conveniently enabled the assembly of a large number of diversified carbazole products with good tolerance of a broad range of functional groups.