Predicting hydration free energies with chemical accuracy: the SAMPL4 challenge

An implicit solvent model described by a non-simple dielectric medium is used for the prediction of hydration free energies on the dataset of 47 molecules in the SAMPL4 challenge. The solute is represented by a minimal parameter set model based on a new all atom force-field, named the liquid simulation force-field. The importance of a first solvation shell correction to the hydration free energy prediction is discussed and two different approaches are introduced to address it: either with an empirical correction to a few functional groups (alcohol, ether, ester, amines and aromatic nitrogen), or an ab initio correction based on the formation of a solute/explicit water complex. Both approaches give equally good predictions with an average unsigned error <1 kcal/mol. Chemical accuracy is obtained.     

Electrophotocatalytic Undirected C−H Trifluoromethylations of (Het)Arenes

Electrophotochemistry has enabled arene C−H trifluoromethylation with the Langlois reagent CF₃SO₂Na under mild reaction conditions. The merger of electrosynthesis and photoredox catalysis provided a chemical oxidant-free approach for the generation of the CF₃ radical. The electrophotochemistry was carried out in an operationally simple manner, setting the stage for challenging C−H trifluoromethylations of unactivated arenes and heteroarenes. The robust nature of the electrophotochemical manifold was reflected by a wide scope, including electron-rich and electron-deficient benzenes, as well as naturally occurring heteroarenes. Electrophotochemical C−H trifluoromethylation was further achieved in flow with a modular electro-flow-cell equipped with an in-operando monitoring unit for on-line flow-NMR spectroscopy, providing support for the single electron transfer processes.     

Gabor Frames in $${\ell }^2({\mathbb {Z}})$$ ℓ 2 ( Z ) and Linear Dependence

We prove that an overcomplete Gabor frame in \({\ell }^2({\mathbb {Z}})\) generated by a finitely supported sequence is always linearly dependent. This is a particular case of a general result about linear dependence versus independence for Gabor systems in \({\ell }^2({\mathbb {Z}})\) with modulation parameter 1 / M and translation parameter N for some \(M,N\in {\mathbb {N}},\) and generated by a finite sequence g in \({\ell }^2({\mathbb {Z}})\) with K nonzero entries.

     

Frame properties of systems arising via iterated actions of operators

Motivated by recent progress in dynamical sampling we prove that every frame which is norm-bounded below can be represented as a finite union of sequences ${\{{(T_j)}^n{\phi }_j\}}_{n=0}^{\infty },j=1,\dots ,J$ for some bounded operators $T_j$ and elements ${\phi }_j$ in the underlying Hilbert space. The result is optimal, in the sense that it turns out to be problematic to replace the collection of generators ${\phi }_1,\dots ,{\phi }_J$ by a singleton: indeed, for linearly independent frames we prove that we can represent the frame in terms of just one system ${\{T^n\phi \}}_{n=0}^{\infty }$, but unfortunately this representation often forces the operator T to be unbounded. Several examples illustrate the connection of the results to typical frames like Gabor frames and wavelet frames, as well as generic constructions in arbitrary separable Hilbert spaces.     

DFT Study of the Molybdenum‐Catalyzed Deoxydehydration of Vicinal Diols

The mechanism of the molybdenum‐catalyzed deoxydehydration (DODH) of vicinal diols has been investigated using density functional theory. The proposed catalytic cycle involves condensation of the diol with an Mo^VI oxo complex, oxidative cleavage of the diol resulting in an Mo^IV complex, and extrusion of the alkene. We have compared the proposed pathway with several alternatives, and the results have been corroborated by comparison with the molybdenum‐catalyzed sulfoxide reduction recently published by Sanz et al. and with experimental observations for the DODH itself. Improved understanding of the mechanism should expedite future optimization of molybdenum‐catalyzed biomass transformations.     

Triggering the Directional Selectivity of a Ring‐Closure Reaction Leads to Pyridoazacarbazoles with Anticancer Properties

We herein describe a facile and versatile synthetic route to the tetracyclic system of 6‐substituted 5,6‐dihydro‐11H‐pyrido[3,2‐i]‐1‐azacarbazoles with promising anticancer properties. These derivatives are built up by an elegant one‐step base‐catalyzed synthetic procedure from commercially available building blocks. One additional step provides the corresponding skeleton hitherto unknown in the literature. The possibility to synthesize a large library of compounds with various substitution patterns utilizing this method underlines the importance of this synthetic procedure.