Refernces
10.1016/j.jfluchem.2019.03.009
The research aims to explore and optimize reactions involving the selective activation and substitution of aromatic fluorine substituents in ortho-fluorinated anilines using Ti(NMe2)4 as a reagent. The study focuses on the regioselective defluoroamination reaction, where a fluorine atom vicinal to the NH2 group of the starting aniline is replaced with an NMe2 group, resulting in the formation of N,N-dimethyl-1,2-phenylenediamine derivatives. The conclusions drawn from the research indicate that the reactivity of these reactions increases with additional ring fluorination, generally following established regiochemical trends. Notably, compounds with fluorines in both the 2- and 6-positions can undergo substitution at both positions given extended reaction times. The chemicals used in this process include ortho-fluorinated anilines, Ti(NMe2)4, mesitylene as the solvent, and bis(4-fluorophenyl)ether as an internal NMR standard. The reactions were found to be general, reasonably efficient, and consistent with established ancillary-fluorine substituent effects, although preliminary experiments showed limited generalization to ortho-fluorinated phenols.
10.1021/jo902669j
The research explores the application of the photo-SN1 reaction on 4-chloroanilines under solar irradiation to develop a metal-free arylation method. The study aims to improve the environmental sustainability of arylations by using sunlight, more environmentally friendly solvents, and reducing the excess of trapping agents. The researchers optimized the reaction conditions using a solar simulator and then tested the reactions under direct sunlight. They found that the process could be scaled up to a gram scale with satisfactory yields, even with higher starting concentrations of halides and lower proportions of trapping agents. The study concludes that solar-induced photo-ArSN1 arylations are a viable and environmentally friendly alternative to traditional metal-catalyzed arylations, with the added benefit of being powered by renewable solar energy. 4-Chloro-N,N-dimethylaniline (1a) serves as the starting material for generating the 4-N,N-dimethylaminophenyl cation upon irradiation. Mesitylene (2a) acts as a p-trap in the reaction. R-Methylstyrene (2b) is another nucleophile used in the study. Allyltrimethylsilane (2c) serves as a nucleophile in the reaction.
10.1039/P29960001367
The research focuses on the thermal decomposition of N-acyl-3,4-dihydro-1H-2,1-benzoxazines, which undergo a retro-Diels-Alder reaction to extrude formaldehyde and form N-acylazaxylylenes. These intermediates then undergo a 6a electrocyclisation to yield 2-substituted-4H-3,1-benzoxazines, rather than a 47c electrocyclisation which would lead to N-acyl-1,2-dihydrobenzazetes. The study provides a detailed characterization of the compounds formed using spectroscopic methods, revealing data inconsistent with previous reports, and suggests that the previously reported structures for these compounds may need to be reevaluated. The chemicals used in this process include a range of N-acyl-3,4-dihydro-1H-2,1-benzoxazines with different substituents (such as N-benzoyl, N-acetyl, N-pivaloyl, etc.), formaldehyde, and various solvents like mesitylene and cyclohexanol for the reactions.
10.1021/ol401538b
The study presents a novel method for the asymmetric synthesis of 2-substituted indolines using bifunctional amino(thio)urea catalysts. The key chemicals involved include the starting materials, which are aniline derivatives bearing an R,?-unsaturated carbonyl moiety, and the bifunctional organocatalysts, specifically quinidine-derived thiourea and urea catalysts. The reaction proceeds through an intramolecular aza-Michael addition, activated by hydrogen bonding, which allows for high enantioselectivity and versatility across a wide range of substrates. The study optimized reaction conditions, finding that less polar aromatic solvents like mesitylene were most effective, and that urea catalysts generally provided better yields and enantioselectivity compared to thiourea catalysts. The scope of substrates was explored, demonstrating the applicability of the method to various electron-rich and electron-poor enones, as well as higher oxidation state substrates like R,?-unsaturated thioesters. The synthesized indolines can be further transformed, highlighting the potential for this method in the synthesis of biologically active compounds.