Reported herein is a visible‐light‐driven intramolecular C−N cross‐coupling reaction under mild reaction conditions (metal‐ and photocatalyst‐free, at room temperature) via a long‐lived photoactive photoisomer complex. This strategy was used to rapidly prepare the N‐substituted polycyclic quinazolinone derivatives with a broad substrate scope (>50 examples) and further exploited to synthesize the natural products tryptanthrin, rutaecarpine, and their analogues. The success of gram‐scale synthesis and solar‐driven transformation, as well as promising tumor‐suppressing biological activity, proves the potential of this strategy for practical applications. Mechanistic investigations, including control experiments, DFT calculations, UV‐vis spectroscopy, EPR, and X‐ray single‐crystal structure of the key intermediate, provides insight into the mechanism.
A visible-light-induced/thiourea-mediated
intramolecular cyclization
of o-nitroarenes under mild conditions is realized
for the first time, which provides an efficient and environmentally
friendly way to access pharmaceutical relevant quinazolinone derivatives.
The reaction can be easily extended to gram level by using a continuous-flow
setup with high efficiency. Mechanistic investigation including control
experiments, transient fluorescence, UV–vis spectra, and DFT
calculations suggests that the formation of active biradical intermediates
via intramolecular single electron transfer (SET) is key stage in
the catalytic cycle.
An efficient metal‐free, (NH4)2S2O8 mediated intramolecular oxidative cyclization for the construction of polycyclic heterocycles was disclosed. A series of polycyclic quinazolinone derivatives with good functional group tolerance were obtained in high yields. The natural products tryptanthrin and rutaecarpine, as well as their derivatives, were easily synthesized by this strategy. A preliminary mechanism study suggested the carbon‐centered radical was involved in the catalytic cycle.
Nanocellulose is an abundant green resource that, owing to the larger surface area, length, and diameter of the fibers, can be used as a framework for loading Ag nanoparticles and serve as substrate for surface enhancement Raman scattering (SERS). These properties would cause the hydroxyl groups on the surface to adsorb the Ag ions and reduce them to Ag seed to form a load fulcrum. This paper presents a convenient and environmentally friendly method for the fabrication of silver-nanocellulose composites (NCF-Ag). A commonly used pesticide, carbendazim (CBZ), was used as a SERS probe to evaluate the properties of NCF-Ag. The results showed that NCF-Ag possesses good homogeneity, reproducibility, and stability. Additionally, CBZ was found to have a low limit of detection (LOD), i.e., 1.0 × 10−8 M, which indicates the possibility for trace analysis. Furthermore, it presents good linearity with R2 = 0.98 at 1007 and 1270 cm−1 in the range from 10−4~10−7 M CBZ.
Two carbon nanotube supported palladium catalysts were prepared using a chemical reduction technique (Pd/CR-CNT) and a conventional impregnation method (Pd/CNT) respectively, and their catalytic performances for Heck reaction were investigated. The catalysts were characterized by TEM and XPS techniques and the products were characterized by 1 H NMR. Research results showed that the (Pd/CR-CNT) catalyst showed a better catalytic activity than the (Pd/CNT) catalyst, owing to better dispersion of palladium nanoparticles and stronger interaction between the active palladium species and carbon nanotube. Meanwhile, the product yield maintained 99.93% of its initial value at five-times re-use, compared with that at the first time use. The catalyst prepared with the chemical reduction method represented a better reusing performance.
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