Metal-Catalyzed C(sp2)−H Functionalization Processes of Phenylalanine- and Tyrosine-Containing Peptides

The site-selective chemical diversification of biomolecules constitutes an unmet challenge of capital importance within medicinal chemistry and chemical biology. The functionalization of otherwise unreactive C-H bonds holds great promise for reducing the reliance on existing functional groups, thereby streamlining chemical syntheses. Over the last years, a myriad of peptide labelling techniques featuring metal-catalyzed C-H functionalization reactions have been developed. Despite the wealth of reports in the field, the site-selective modification of both phenylalanine (Phe) and tyrosine (Tyr) compounds upon metal catalysis remain comparatively overlooked. This review highlights these promising tagging strategies, which generally occur through the formation of challenging 6-membered metallacycles and enable the late-stage diversification of peptides in a tailored fashion.A. Correa is grateful to Ministerio de Ciencia e Innovacion (RTI2018-093721-B-I00, MCI/AEI/FEDER, UE) and Basque Government (IT1033-16) for financial support. He also kindly acknowledges the GEQO group of the RSEQ for the GEQO Young Research Award 2019. Likewise, he sincerely thanks all co-workers for their dedication and invaluable contribution

Selective C(sp2)−H Halogenation of "click" 4-Aryl-1,2,3-triazoles

Selective bromination reactions of “click compounds” are described. Electron-neutral and electron-deficient arenes selectively undergo unprecedented Pd-catalyzed C–H ortho-halogenations assisted by simple triazoles as modular directing groups, whereas electron-rich arenes are regioselectively halogenated following an electrophilic aromatic substitution reaction pathway. These C–H halogenation procedures exhibit a wide group tolerance, complement existing bromination procedures, and represent versatile synthetic tools of utmost importance for the late-stage diversification of “click compounds”. The characterization of a triazole-containing palladacycle and density functional theory studies supported the mechanism proposal.We are grateful to Gobierno Vasco (ELKARTEK_KK-2015/0000101; IT_1033-16) and UPV/EHU (GIU15/31) for financial support. A. C. thanks MINECO for a Ramón y Cajal research contract (RYC-2012-09873). Cost-CHAOS action is also acknowledged

Современные методики оценки взаимодействия акторов инновационных систем

The article deals with methods of actor`s evaluation. Practice shows that in Russia today, the main problem of the transition to the innovative way of development is the lack of an effective system of interaction between actors in the innovation system. To date, there is no single methodology for assessing the processes that take place between the actors of the innovation system

Triazole-Directed Pd-Catalyzed C(sp2)–H Oxygenation of Arenes and Alkenes

Selective Pd-catalyzed C(sp2)–H oxygenation of 4-substituted 1,2,3-triazoles is described. Unlike previous metal-catalyzed C–H functionalization events, which preferentially occur at the activated heterocyclic C–H bond, the regioselective oxygenation of the arene/alkene moiety is now achieved featuring the unconventional role of a simple triazole scaffold as a modular and selective directing group.MINECO for a Ramon y Cajal research contract (RYC-2012-09873)

Распределение примесных ионов в поверхностных слоях диэлектриков, модифицированных ионными пучками

The results of studies of impurity ions distribution in surface layers of dielectric modified by ion beams are presented. Depth profiles were measured by secondary ion mass spectrometry method. Computer simulations of the expected ion depth profile were carried out using the TRIM program. The alumina ceramic implanted with Ti ions at energy 50 keV and zirconium ceramic implanted with Al ions at energy 78 keV were investigated in our work

Site-Selective Trifluoromethylation Reactions of Oligopeptides

Site-selective chemical modifications that target proteinogenic amino acid residues complement the methods entailing genetic manipulation, thereby allowing straightforward and rapid access to engineered proteins. The incorporation of the trifluoromethyl group into amino acids within a peptide sequence results in relevant peptidomimetics with unique biomedicinal properties. As a result, the last decade has witnessed the development of a powerful set of protocols toward the selective trifluoromethylation of small-to-medium size peptides and proteins in a late-stage fashion. This minireview seeks to highlight those particularly compelling cases published in the last years.We are grateful to MINECO (RTI2018‐093721‐BI00) and Basque Government (IT1033‐16) for financial support. I. G. thanks Basque Government for a predoctoral fellowshi

Cu-Catalyzed Site-Selective C(sp2)–H Radical Trifluoromethylation of Tryptophan Containing Peptides

Site-selective functionalization of C–H bonds within a peptide framework poses a challenging task of paramount synthetic relevance. Herein, we report an operationally simple C(sp2)–H trifluoromethylation of tryptophan (Trp)-containing peptides. This fluorination technique is characterized by its chirality preservation, tolerance of functional groups, and scalability and exhibits chemoselectivity for Trp residues over other amino acid and heterocyclic units. As a result, it represents a sustainable tool toward the late-stage peptide modification and protein engineering.We are grateful to MINECO (RTI2018-093721-B-I00) and the Basque Government (IT1033-16) for financial support. I.G. thanks the Basque Government for a predoctoral fellowship. We are thankful for technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF). Cost-CHAOS action (CA15106) is also acknowledged

Деформации корпоративной собственности в российской экономике

Установлено, что собственность в отечественной экономике носит квазикорпоративный характер. Определены ключевые параметры данного института, показаны механизмы его воспроизводства