Selective skeletal editing of polycyclic arenes using organophotoredox dearomative functionalization

Reactions that lead to destruction of aromatic ring systems often require harsh conditions and, thus, take place with poor selectivities. Selective partial dearomatization of fused arenes is even more challenging but it can be a strategic approach to creating versatile, complex polycyclic frameworks. Herein we describe a general organophotoredox approach for the chemo- and regioselective dearomatization of structurally diverse polycyclic aromatics, including quinolines, isoquinolines, quinoxalines, naphthalenes, anthracenes and phenanthrenes. The success of the new method for chemoselective oxidative rupture of aromatic moieties relies on precise manipulation of the electronic nature of the fused polycyclic arenes. Experimental and computational results show that the key to overcoming the intrinsic thermodynamic and kinetic unfavorability of the dearomatization process is an ultimate hydrogen atom transfer (HAT) step, which enables dearomatization to predominate over the otherwise favorable aromatization pathway. We show that this strategy can be applied to rapid synthesis of biologically valued targets and late-stage skeletal remodeling en route to complex structures.

7 Electrochemically Generated Nitrogen-Centered Radicals

Nitrogen-centered radicals are versatile reactive intermediates for organic synthesis. This chapter describes recent progress in the electrochemical generation and reactions of nitrogen-centered radicals. Under electrochemical conditions, various nitrogen-centered radicals are generated through electrolysis of readily available precursors such as N—H bonds or azides. These reactive intermediates undergo addition reactions to π-systems or hydrogen-atom abstraction to generate various nitrogen-containing compounds.

Photoinduced C-H monofluoroalkenylation with gem-difluoroalkenes through hydrogen atom transfer in batch and flow

Direct monofluoroalkenylation of C-H bonds are straightforward approaches for accessing multisubstituted monofluoroalkenes. However, general methods for the monofluoroalkenylation of C(sp3)-H bonds remain challenges. Here we report the development of a...

Hydrogen-atom and oxygen-atom transfer reactivities of iron(iv)-oxo complexes of quinoline-substituted pentadentate ligands

The reactivities of Fe(iv) oxido complexes of two pentadentate ligands are related to steric and electronic properties of the ligands.

Theoretical Investigations of State Specific Hydrogen Atom Transfer in 8-Formyl-7-hydroxy-4-methylcoumarin

Excited state intramolecular hydrogen transfer (ESIHT) reaction of 8-formyl-7-hydroxy-4-methyl coumarin (FC) in its pure and hydrated state FC-(H2O)4 (FCH) has been studied by implementing state specific time dependent density functional theory (SS-TDDFT) along with the effective fragment potential (EFP1) method for solvation with discrete water molecules. The intramolecular hydrogen bond formed between hydroxyl hydrogen (H18) and formyl oxygen (O15) and intermolecular hydrogen bonds formed due to microsolvation were explored. The studies of electrostatic potential, natural charge analysis, difference electron density map and UV-Vis spectra of both FC and FCH molecules establish the intramolecular charge transfer (ICT) states of the molecules. The vertical excitation from S0 to S1 state causes the transfer of hydroxyl hydrogen to formyl oxygen and from S1 to S3 causes the transfer of the hydrogen atom back to hydroxyl oxygen. Potential energy surface scans along intramolecular hydrogen bonding at the ground and excited states confirm the state specific ESIHT reaction in both FC and FCH molecules.

Исследование структурного совершенства монокристаллов ниобата лития разного состава и генезиса методом ИК спектроскопии в области валентных колебаний водородных связей

We have analyzed complex defects due to the presence of hydrogen bonds in the crystal structure in nominally pure lithium niobate crystals with different Li/Nb ratio, in crystals alloyed with magnesium and zinc in a wide concentration range (LiNbO3 : Mg (0.19-5.91 mol.% MgO) and LiNbO3 : Zn (0.04-6.5 mol. % ZnO)) and in the double-alloyed crystals (LiNbO3 : Y(0.24) : Mg(0.63 wt. %) and LiNbO3 : Gd (0.25) : Mg(0.75 wt. %)), obtained by technology of direct melt alloying, and also in the double-alloyed crystal (LiNbO3 : Mg(5. 05 mol.% MgO) : Fe(0.009 mol.% Fe2O3)) grown from a charge synthesized using the technology of homogeneous alloying with magnesium and iron Nb2O5. We revealed the influence of doping impurities on the concentration of OH-groups, the type and localization of complex defects in the crystal structure. The change in the number of hydrogen atom positions in the structure of the LiNbO3 crystal allow us to judge with sufficient accuracy whether the crystal composition is stoichiometric or congruent. For doped crystals of different compositions data were obtained testifying to changes in the character of complexation of OH-groups with point defects of the cationic sublattice with formation of defects: MеLi-OH-, MеLi-MеNb-OН. A change in the mechanism of entry of the dopant cation into the structure dramatically affects the change in the properties of the crystal.The difference in the frequencies (and, correspondingly, in the values of the quasi-elastic constants of the O-H bonds) in the spectrum of a congruent crystal and doped crystals can also be contributed by differences in the electronegativity and ionic radii of the principal and doping cations.

Quantum chemical study on the interaction of arginine with silica surface

The structure and energy characteristics of structures formed during arginine adsorption on silica surface from aqueous solution were studied by the density functional theory (B3LYP) method using a valence-split basis set 6-31++G(d,p) within the continuous solvent model (PCM) and supermolecular approximation. The equilibrium structural and energy parameters of the protonated arginine molecule in the gas phase dependent on the location of the hydrogen atom are considered including those of two possible zwitterions. The structure of the arginine ion Н2А+, which is formed when a proton attaches to a molecule or zwitterion of a given amino acid, has been elucidated. To determine the deprotonation constant of the carboxyl group in an acidic medium, the complexes of the arginine molecule (AH32+) in the state with undissociated and deprotonated carboxyl groups are considered. The simulation of the acid medium was performed by taking into account the interaction with two hydrated HCl ion pairs, which provided the protonation of the a-amino group and the nitrogen atom of amino group within the guanidine group. In the study on the interaction of an arginine molecule with silica surface in an aqueous medium, complexes containing a Si8O12(OH)7O– ion with a deprotonated silanol group, six water molecules, and an arginine molecule with a deprotonated carboxyl group were considered. It has been found that the arginine molecule is most likely to be adsorbed on slica surface with formation of hydrogen bonds between the hydrogen atoms of the a-amino group and the oxygen atom of the deprotonated silanol group. In this case, the formation of a hydrogen bond between the oxygen atom of the carboxyl group and the hydrogen atom of the neighboring silanol group is possible. Slightly less likely is adsorption of arginine molecules due to interaction of the guanidine group with silanol groups of the surface. According to the calculated data, the adsorption of the zwitterionic form of the arginine molecule from the aqueous solution is equally likely to occur due to interaction of silanol groups of silica surface with both the carboxyl group and the guanidine group.