Catalytic ipso-Nitration of Organosilanes Enabled by Electrophilic N-Nitrosaccharin Reagent.

Nitroaromatic compounds represent one of the essential classes of molecules that are widely used as feedstock for the synthesis of intermediates, the preparation of nitro-derived pharmaceuticals, agrochemicals, and materials on both laboratory and industrial scales. We herein disclose the efficient, mild, and catalytic ipso-nitration of organotrimethylsilanes, enabled by an electrophilic N-nitrosaccharin reagent and allows chemoselective nitration under mild reaction conditions, while exhibiting remarkable substrate generality and functional group compatibility. Additionally, the reaction conditions proved to be orthogonal to other common functionalities, allowing programming of molecular complexity via successive transformations or late-stage nitration.

Electron-Driven Nitration of Unsaturated Hydrocarbons.

Herein, we introduce an electrochemically assisted generation of nitryl radicals from ferric nitrate under mild reaction conditions using a simple setup with inexpensive graphite and stainless-steel electrodes. The mechanism of the reaction is supported by detailed spectroscopic and experimental studies. Powered by electricity and driven by electrons, the synthetic diversity of this reaction has been demonstrated through the development of highly efficient nitration protocols of various unsaturated hydrocarbons.

Photoredox Activation of Anhydrides for the Solvent-Controlled Switchable Synthesis of gem-Difluoro Compounds.

The incorporation of the gem-difluoromethylene (CF ) group into organic frameworks is highly sought due to the influence of this unit on the physicochemical and pharmacological properties of molecules. Herein we report an operationally simple, mild, and switchable protocol to access various gem-difluoro compounds that employs chlorodifloroacetic anhydride (CDFAA) as a low-cost and versatile fluoroalkylating reagent. Detailed mechanistic studies revealed that electron-transfer photocatalysis triggers mesolytic cleavage of a C-Cl bond generating a gem-difluoroalkyl radical.

Deployment of Sulfinimines in Charge-Accelerated Sulfonium Rearrangement Enables a Surrogate Asymmetric Mannich Reaction.

β-Amino acid derivatives are key structural elements in synthetic and biological chemistry. Despite being a hallmark method for their preparation, the direct Mannich reaction encounters significant challenges when carboxylic acid derivatives are employed. Indeed, not only is chemoselective enolate formation a pitfall (particularly with carboxamides), but most importantly the inability to reliably access α-tertiary amines through an enolate/ketimine coupling is an unsolved problem of this century-old reaction.

As Similar As Possible, As Different As Necessary - On-Site Laboratory Teaching during the COVID-19 Pandemic.

Most of the available information on studying under the challenging conditions brought about by the COVID-19 pandemic emphasizes a variety of aspects on how to digitalize the whole teaching process. Thus, several useful and potentially game-changing strategies have been reported recently. In contrast to the digitalization of teaching, in this article, we focus on the reverse process: transitioning back to offline teaching, which is unavoidable especially for the acquisition of practical skills during chemistry studies.

Free-radical cyclization approach to polyheterocycles containing pyrrole and pyridine rings.

A wide range of derivatives with new pyrido[2,1-]pyrrolo[3,4-]isoquinoline skeleton was synthesized by free-radical intramolecular cyclization of -bromophenyl-substituted pyrrolylpyridinium salts using the (TMS)SiH/AIBN system. The cyclization provides generally good yields of pyrido[2,1-]pyrrolo[3,4-]isoquinoline hydrobromides having no additional radical-sensitive substituents. The free bases can be obtained from the synthesized hydrobromides in quantitative yield by basification at room temperature.

Synthesis of Pyrrolotriazoloisoquinoline Frameworks by Intramolecular Cu-Mediated or Free Radical Arylation of Triazoles.

The cyclization of (2-bromophenyl)pyrrolyl-1,2,4-triazoles via copper-mediated intramolecular direct C-arylation of 1,2,4-triazoles was first accomplished under triazole-NHC control to give unknown fused heterocyclic skeletons, pyrrolo[3,2-c][1,2,4]triazolo[5,1-a] or [3,4-a]isoquinolines. The primary products underwent a triazole ring opening under the basic arylation conditions, providing N-(1H-pyrrolo[3,2-c]isoquinolin-5-yl)cyanamides. The formation of the cyanamides from isomeric pyrrolo[3,2-c][1,2,4]triazolo[3,4-a]isoquinolines involves, besides the triazole ring opening, the unusual migration of the cyano group.

[Status and development prospects of radiological health in the Navy].

More than 7.5 thousands of people work as military and civilian personnel and have an access to a lot of sources of ionizing radiation on ships and vessels, at coastal units and institutions of the Navy. This fact determines the importance of radiation safety and medical preventive measures on naval fleets.

[Seasonal variations of hemodynamic parameters in young men of Northern region].

The seasonal peculiarities of cardiovascular system in youngsters of northern region are analyzed. It is showed that tension of systematic hemodynamics during the winter is connected with increase of contribution of vascular and cardio components in support of adaptive reaction of cardiovascular system. The reduction of amount of addictions provides mobilization of functional reserves of organism.

[Psychophysiological factors of maintaining mental health in individuals with extreme professions].

The research aims to establish psychophysiological factors of maintaining health in individuals, in whose professional activities on the substantial level there is an extreme component. During the research it was established that the effective work of regulatory mechanisms contributes to the formation of the mental health, which stability is not a factor contributing to the restoration of psychophysiological resources.

[Quality of a life of military seamen of Northern fleet].

Research of quality of a life of military seamen with use of the Russian-speaking version of the general questionnaire of health "Medical Outcomes Study-Short Forms" (SF-36) is conducted. 600 military men at the age from 18 till 55 years are surveyed. Military seamen have highly appreciated the quality of a life.

[Regularity of psychophysiological adaptation to military-professional activity among staff of Northern Fleet].

There were examined regularities of psycho-physiological adaptation of different categories of military-navy specialists, were detected periods of maximum decrease of compensation abilities among sailor-men and staff reserve of Naval Fleet from students. Were educed psycho-physiological strategies of adaptation of military-navy specialists in dependence of reference level of adaptation capabilities. Was detected the influence on the process of psycho-physiological adaptation to service activity of young specialists of a complex of psychological and social factors.

[Peculiarities of psychophysiological status of flying staff of fighter aircraft of land basing].

It was investigated the influence of professional activity on psychophysiological peculiarities of fighter pilot of different types of aircraft of land basing and afloat aircraft. As a result of investigation, it was determined that on base of social parameters they are equal. Airmen of the aviation of land basing have a similar personality profile, but different types of interpersonal relations.

[Psychophysiological and social-and-psychological aspects of adaptation to military service in the European North of Russia in the servicemen called from different regions].

The article presents the investigational results of psychophysiological and social-and-psychological adaptation to military service in conditions of the European North of Russia in servicemen called up from different regions. During the first 6 months the positive dynamics concerning the communicative and personal adaptation potential and behavioral regulation was noted in all 239 servicemen. It was established that the representatives from northern region have lower potential possibilities of social-and-psychological adaptation to military service in the European North of Russia than the youths called up from other regions.