Catalytic Behavior of Mono-N-Protected Amino-Acid Ligands in Ligand-Accelerated C−H Activation by Palladium(II)

Mono-N-protected amino acids (MPAAs) are increasingly common ligands in Pd-catalyzed C−H functionalization reactions. Previous studies have shown how these ligands accelerate catalytic turnover by facilitating the C−H activation step. Here, it is shown that MPAA ligands exhibit a second property commonly associated with ligand-accelerated catalysis: the ability to support catalytic turnover at substoichiometric ligand-to-metal ratios. This catalytic role of the MPAA ligand is characterized in stoichiometric C−H activation and catalytic C−H functionalization reactions. Palladacycle formation with substrates bearing carboxylate and pyridine directing groups exhibit a 50–100-fold increase in rate when only 0.05 equivalents of MPAA are present relative to Pd^II. These and other mechanistic data indicate that facile exchange between MPAAs and anionic ligands coordinated to Pd^II enables a single MPAA to support C−H activation at multiple Pd^II centers.     

Critical Assessment of the DFT + U Approach for the Prediction of Vanadium Dioxide Properties

In a previous study (Stahl and Bredow, Chem. Phys. Lett. 2018, 695, 28–33), we have studied structural, energetic, and electronic properties of two vanadium dioxide VO₂ polymorphs with modified global and range-separated hybrid functionals. Since hybrid methods are computationally demanding, we evaluate the computationally more efficient DFT + U method in the present study. We assessed the widely used Dudarev PBE + U approach with a literature value of the effective Hubbard parameter U_eff = 3.4 eV. We compared the PBE + U results for the two VO₂ polymorphs with our previous results, a self-consistent hybrid functional sc-PBE0, and the meta-GGA functional SCAN. It was found that the PBE + U method yields a strongly distorted monoclinic phase and does not reproduce the metal-to-insulator transition of VO₂ correctly, even with modified values of U_eff. On the other hand, sc-PBE0 and SCAN describe the relative stability and the electronic structure of both polymorphs correctly and also provide reasonable lattice parameters. The functional SCAN yields the optimal balance between computational efficiency and accuracy. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.     

Advances towards Cell-Specific Gene Transfection: A Small-Molecule Approach Allows Order-of-Magnitude Selectivity

A transfection vector that can home in on tumors is reported. Whereas previous vectors that allow moderately cell selective gene transfection used larger systems, this small-molecule approach paved the way for precise structure-activity relationship optimization. For this, biotin, which mediates cell selectivity, was combined with the potent DNA-binding motif tetralysine-guanidinocarbonypyrrol via a hydrophilic linker, thus enabling SAR-based optimization. The new vector mediated biotin receptor (BR)-selective transfection of cell lines with different BR expression levels. Computer-based analyses of microscopy images revealed a preference of one order of magnitude for the BR-positive cell lines over the BR-negative controls.     

Green and sustainable chemistry in Latin America: Which type of research is going on? And for what?

Green (and sustainable?) frame around ‘Inverted America’ (adapted from Torres García, 1943, Museo Juan Manuel Blanes, Montevideo, CC BY 4.0).

1. Download : Download high-res image (122KB)
2. Download : Download full-size image

     

Acetyl Methyl Torsion in N‐Ethylacetamide: A Challenge for Microwave Spectroscopy and Quantum Chemistry

The gas‐phase structures and parameters describing acetyl methyl torsion of N‐ethylacetamide are determined with high accuracy, using a combination of molecular beam Fourier‐transform microwave spectroscopy and quantum chemical calculations. Conformational studies at the MP2 level of theory yield four minima on the energy surface. The most energetically favorable conformer, which possesses C₁ symmetry, is assigned. Due to the torsional barrier of 73.4782(1) cm^?1 of the acetyl methyl group, fine splitting up to 4.9 GHz is found in the spectrum. The conformational structure is not only confirmed by the rotational constants, but also by the orientation of the internal rotor. The ¹⁴N quadrupole hyperfine splittings are analyzed and the deduced coupling constants are compared with the calculated values.     

Quinone‐Catalyzed Selective Oxidation of Organic Molecules

Quinones are common stoichiometric reagents in organic chemistry. Para‐quinones with high reduction potentials, such as DDQ and chloranil, are widely used and typically promote hydride abstraction. In recent years, many catalytic applications of these methods have been achieved by using transition metals, electrochemistry, or O₂ to regenerate the oxidized quinone in situ. Complementary studies have led to the development of a different class of quinones that resemble the ortho‐quinone cofactors in copper amine oxidases and mediate the efficient and selective aerobic and/or electrochemical dehydrogenation of amines. The latter reactions typically proceed by electrophilic transamination and/or addition‐elimination reaction mechanisms, rather than hydride abstraction pathways. The collective observations show that the quinone structure has a significant influence on the reaction mechanism and has important implications for the development of new quinone reagents and quinone‐catalyzed transformations.