Recent Advances In Synthetic Chemistry Research Articles

Radical generation enabled by photoinduced N-O bond fragmentation.

Recent advances in synthetic chemistry have seen a resurgence in the development of methods for visible light-mediated radical generation. Herein, we report the development of a photoactive ester based on a quinoline N-oxide core structure, that provides a strong oxidant in its excited state. The heteroaromatic N-oxide provides access to primary, secondary, and tertiary radical intermediates, and its application toward the development of a photochemical Minisci alkylation is reported.

ChemInform Abstract: The Chemistry of Ynol and Thioynol Ethers

AbstractReview: 64 refs.

Recent Advances in Synthetic Chemistry of Diabetic Research.

Diseases started even before the existence of human beings. Therefore, when the civilization began, the biggest threats for human were diseases. Man has made several sincere attempts for the search of new drugs in order to cure and control different diseases. Type 2 diabetes mellitus (T2DM) is a chronic metabolic disorder that accounts for about 85-95% of all diagnosed cases of diabetes. It is characterized by abnormalities in glucose homeostasis in many organs, and is associated with considerable morbidity and mortality. Extensive research has been carried out using rational drug design to identify and optimize new leads for molecular targets of T2DM, which include Heterocyclic compounds, metal complexes, H3 receptor antagonists, glucagon receptor antagonists and human incretin-degrading enzyme dipeptidyl peptidase IV inhibitors.

Gold Nanoparticles: Recent Advances in the Biomedical Applications

Among the multiple branches of nanotechnology applications in the area of medicine and biology, Nanoparticle technology is the fastest growing and shows significant future promise. Nanoscale structures, with size similar to many biological molecules, show different physical and chemical properties compared to either small molecules or bulk materials, find many applications in the fields of biomedical imaging and therapy. Gold nanoparticles (AuNPs) are relatively inert in biological environment, and have a number of physical properties that are suitable for several biomedical applications. For example, AuNPs have been successfully employed in inducing localized hyperthermia for the destruction of tumors or radiotherapy for cancer, photodynamic therapy, computed tomography imaging, as drug carriers to tumors, bio-labeling through single particle detection by electron microscopy and in photothermal microscopy. Recent advances in synthetic chemistry makes it possible to make gold nanoparticles with precise control over physicochemical and optical properties that are desired for specific clinical or biological applications. Because of the availability of several methods for easy modification of the surface of gold nanoparticles for attaching a ligand, drug or other targeting molecules, AuNPs are useful in a wide variety of applications. Even though gold is biologically inert and thus shows much less toxicity, the relatively low rate of clearance from circulation and tissues can lead to health problems and therefore, specific targeting of diseased cells and tissues must be achieved before AuNPs find their application for routine human use.

ChemInform Abstract: Coordination Chemistry of Group 13 Monohalides

AbstractReview: 134 refs.

Coordination chemistry of group 13 monohalides

The Group 13 monohalides, EX, are valence isoelectronic with the key textbook diatomic molecules CO and N2; recent advances in synthetic chemistry leading to the isolation of transition metal complexes containing such fragments as ligands are appraised, together with studies of the electronic structure and reactivity of the coordinated molecules.

Electronic structure and spectroscopy of “superoxidized” iron centers in model systems: theoretical and experimental trends

Recent advances in synthetic chemistry have led to the discovery of "superoxidized" iron centers with valencies Fe(v) and Fe(vi) [K. Meyer et al., J. Am. Chem. Soc., 1999, 121, 4859-4876; J. F. Berry et al., Science, 2006, 312, 1937-1941; F. T. de Oliveira et al., Science, 2007, 315, 835-838.]. Furthermore, in recent years a number of high-valent Fe(iv) species have been found as reaction intermediates in metalloenzymes and have also been characterized in model systems [C. Krebs et al., Acc. Chem. Res., 2007, 40, 484-492; L. Que, Jr, Acc. Chem. Res., 2007, 40, 493-500.]. These species are almost invariably stabilized by a highly basic ligand X(n-) which is either O(2-) or N(3-). The differences in structure and bonding between oxo- and nitrido species as a function of oxidation state and their consequences on the observable spectroscopic properties have never been carefully assessed. Hence, fundamental differences between high-valent iron complexes having either Fe=O or Fe=N multiple bonds have been probed computationally in this work in a series of hypothetical trans-[FeO(NH(3))(4)OH](+/2+/3+) (1-3) and trans-[FeN(NH(3))(4)OH](0/+/2+) (4-6) complexes. All computational properties are permeated by the intrinsically more covalent character of the Fe=N multiple bond as compared to the Fe=O bond. This difference is likely due to differences in Z* between N and O that allow for better orbital overlap to occur in the case of the Fe=N multiple bond. Spin-state energetics were addressed using elaborate multireference ab initio computations that show that all species 1-6 have an intrinsic preference for the low-spin state, except in the case of 1 in which S=1 and S=2 states are very close in energy. In addition to Mössbauer parameters, g-tensors, zero-field splitting and iron hyperfine couplings, X-ray absorption Fe K pre-edge spectra have been simulated using time-dependent DFT methods for the first time for a series of compounds spanning the high-valent states +4, +5, and +6 for iron. A remarkably good correlation of these simulated pre-edge features with experimental data on isolated high-valent intermediates has been found, allowing us to assign the main pre-edge features to excitations into the empty Fe d(z(2)) orbital, which is able to mix with Fe 4p(z), allowing an efficient mechanism for the intensification of pre-edge features.