Micellar photocatalysis enables divergent C-H arylation and N dealkylation of benzamides via N-acyliminium cations

Micellar photocatalysis has recently opened new avenues to activate strong carbon halide bonds. So far, however, it has mainly explored strongly reducing conditions restricting the available chemical space to radical or anionic reactivity. Here, we demonstrate a radical-polar crossover process involving cationic intermediates, which enables chemodivergent modification of chlorinated benzamide derivatives via either C H arylation or N dealkylation. The catalytic system operates under mild conditions employing methylene blue as a photocatalyst and blue LEDs as the light source. Factors determining the reactivity of substrates and preliminary mechanistic studies are presented.

Identification of the Mechanism of Synthesis of SDRL Rubber

Modelling and identification of the synthesis of SDRL rubber in the presence of toluene and modifier was carried out. The mechanism of the polymerization of butadiene on the lithium catalytic system. One of the most characteristic differences between the processes of ionic, in particular, anionic, polymerization and radical polymerization is that even when using initiators that seem to be individual, several forms of active centres, that differ in their reactivity, can simultaneously be present in systems.

Breaking The Monotony: Cobalt and Maleimide as a New Entrant to the Catellani Reaction

A catalytic system was discovered for the intramolecular C-H amidation of N-phenoxy acetamide derivatives. For the first time, a cobalt catalyst was employed for the Catellani reaction. Additionally, a monocyclic olefin, maleimide, was used as a transient mediator in place of bicyclic norbornenes. Maleimide promotes a Co(III) intermediate to undergo oxidative addition into the O–N bond to form a Co(V) nitrene species and subsequently directs nitrene addition to the ortho position. A plausible mechanism for the transformation is proposed, supported by experimental and density functional theory (DFT) computational studies. Further, the synthetic utility of this methodology was demonstrated via the ortho-amidation of estrone.

Calculation and Analysis of the Molecular Weight Characteristics of the Polymer in the Synthesis of Butyl Rubber

The article compiled a mathematical model of the cationic copolymerization of isobutylene and isoprene using a catalyst AlCl3 in a CH3Cl solution, including the reactions of initiation, chain growth, chain transfer to the monomer, and chain termination. The molecular weight characteristics of butyl rubber synthesized in methyl chloride using a catalytic system based on aluminum trichloride have been investigated. Relationships are obtained for calculating the moments of the molecular weight characteristics of butyl rubber. The effect of the concentration of the initiator on the conversion versus time was investigated.

Enzymatic Activity of Individual Bioelectrocatalytic Viral Nanoparticles: Dependence of Catalysis on the Viral Scaffold and its Length

The enzymatic activity of tobacco mosaic virus (TMV) nanorod particles decorated with an integrated electro-catalytic system, comprising the quinoprotein glucose-dehydrogenase (PQQ-GDH) enzyme and ferrocenylated PEG chains as redox mediators, is...

Cu/Fe-Mediated N(sp2)-arylation/alkenylation of pyridines with aryl-/alkenylboronic acids to yield versatile cationic materials

Cu/Fe-mediated arylation of pyridines with arylboronic acids, featuring low-cost catalytic system and easy operation, is disclosed. A series of length-controllable linear (the number of aryls ranges from 2 to 6)...