Non-conventional Behavior of a 2,1-Benzazaphosphole: Heterodiene or Hidden Phosphinidene?

Invited for the cover of this issue are Zoltán Benkő, Libor Dostál and co-workers at the University of Pardubice and the Budapest University of Technology and Economics. The image depicts signs for the two different pathways representing the two differing reaction types which were clearly observed for 2,1-benzazaphosphole. Read the full text of the article at 10.1002/chem.202101686 .     

Selective Reduction of the N-O Bond in Heteroaromatic N-Oxides by TiCl4/SnCl2

Heteroaromatic N-oxides bearing various functionalities are readily and selectively converted under mild conditions into the corresponding bases using TiCl₄/SnCl₂.     

Photomechanical Actuation of Ligand Geometry in Enantioselective Catalysis

A catalyst that couples a photoswitch to the biaryl backbone of a chiral bis(phosphine) ligand, thus allowing photochemical manipulation of ligand geometry without perturbing the electronic structure is reported. The changes in catalyst activity and selectivity upon switching can be attributed to intramolecular mechanical forces, thus laying the foundation for a new class of catalysts whose selectivity can be varied smoothly and in situ over a useful range by controlling molecular stress experienced by the catalyst during turnover. Forces on the order of 100 pN are generated, thus leading to measurable changes in the enantioselectivities of asymmetric Heck arylations and Trost allylic alkylations. The differential coupling between applied force and competing stereochemical pathways is quantified and found to be more efficient for the Heck arylations.     

Highly Chemoselective Synthesis of Indolizidine Lactams by SmI2‐Induced Umpolung of the Amide Bond via Aminoketyl Radicals: Efficient Entry to Alkaloid Scaffolds

Samarium(II) iodide enables a wide range of highly chemoselective umpolung radical transformations proceeding by electron transfer to carbonyl groups; however, cyclizations of important nitrogen‐containing precursors have proven limited due to their prohibitive redox potential. Herein, we report the first reductive cyclizations of unactivated cyclic imides onto N‐tethered olefins using SmI₂/H₂O. This new umpolung protocol leads to the rapid synthesis of nitrogen‐containing heterocycles that are of particular significance as precursors to pharmaceutical pharmacophores and numerous classes of alkaloids. The reaction conditions tolerate a wide range of functional groups. Excellent chemoselectivity is observed in the cyclization over amide and ester functional groups. Such unconventional reactivity has important implications for the design and optimization of new bond‐forming reactions by umpolung radical processes. The reaction advances the SmI₂ cyclization platform to the challenging unactivated N‐tethered acyl‐type radical precursors to access nitrogen‐containing architectures.     

Facile synthesis of potassium tetrathiooxalate – The “true” monomer for the preparation of electron-conductive poly(nickel-ethylenetetrathiolate)

Herein, aiming at optimization of the polymerization process leading to a family of hole- and electron-conducting 1,1,2,2-ethenetetrathiolate-based polymers, such as poly(nickel-1,1,2,2-ethenetetrathiolate), poly[K_x(Ni-ett)], we investigated transformations of the monomer precursor 1,3,4,6-tetrathiapentalene-2,5-dione (TPD) occurring under polymerization conditions. We found that only one ring of TPD opens upon its reaction with potassium methoxide under inert conditions at room temperature which leads to the formation of potassium 2-oxo-1,3-dithiol-4,5-dithiolate (K₂[3]). Heating of K₂[3] under reflux in methanol solution under inert conditions opens the second ring, however the resulting product is not potassium ethenetetrathiolate (K₄[2]), the product of an exhaustive methanolysis of TPD, but potassium tetrathiooxalate (K₂[4]), the product of the decarbonylation of K₂[3]. Preliminary experiments reveal that the involvement of K₂[4] in the polymerization process is beneficial for reproducible formation of high quality 1,1,2,2-ethenetetrathiolate-based polymers suitable for thermoelectric applications.     

Acid-Catalyzed RNA-Oligomerization from 3’,5’-cGMP

The assembly of ancient informational polymers from nucleotide precursors is the central challenge of life's origin on our planet. Among the possible solutions, dry polymerization of 3’,5’-cyclic guanosine monophosphate (3’,5’-cGMP) has been proposed as a candidate to create oligonucleotides of 15–20 units in length. However, the reported sensitivity of the reaction to the presence of cations raised questions of whether this chemistry could be relevant in a geological context. The experiments in this study show that the presence of cations is not restrictive as long as the reaction is conducted in an acidic environment, in contrast to previous reports that suggested optimal conditions at pH 9.     

On new effects of wheel-rail interaction

The paper is devoted to the experimental, theoretical analysis and computer simulation of influence of elastic properties of contact stiffness and wheel-plate stiffness on the forces of vehicle-track interaction. Three types of wheels are considered with different contact stiffness and wheel-plate design. Exemplary simulation of freight car interaction with track which posses one corrugated rail for each type of wheel is presented.     

Strategies for spectrum slicing based on restarted Lanczos methods

In the context of symmetric-definite generalized eigenvalue problems, it is often required to compute all eigenvalues contained in a prescribed interval. For large-scale problems, the method of choice is the so-called spectrum slicing technique: a shift-and-invert Lanczos method combined with a dynamic shift selection that sweeps the interval in a smart way. This kind of strategies were proposed initially in the context of unrestarted Lanczos methods, back in the 1990’s. We propose variations that try to incorporate recent developments in the field of Krylov methods, including thick restarting in the Lanczos solver and a rational Krylov update when moving from one shift to the next. We discuss a parallel implementation in the SLEPc library and provide performance results.