Stereoselective Thioconjugation by Photoinduced Thiol-ene Coupling Reactions of Hexo- and Pentopyranosyl d- and l-Glycals at Low-Temperature-Reactivity and Stereoselectivity Study.

A comprehensive optimization and mechanistic study on the photoinduced hydrothiolation of different d- and l- hexo- and pentoglycals with various thiols was performed, at the temperature range of RT to -120 °C. Addition of thiols onto 2-substituted hexoglycals proceeded with complete 1,2-cis-α-stereoselectivity in all cases. Hydrothiolation of 2-substituted pentoglycals resulted in mixtures of 1,2-cis-α- and -ß-thioglycosides of varying ratio depending on the configuration of the reactants. Hydrothiolation of unsubstituted glycals at -80 °C proceeded with excellent yields and, except for galactal, provided the axially C2-S-linked isomers with high selectivity. Cooling was always beneficial to the efficacy, increased the yields and in most cases significantly raised the stereoselectivity. The suggested mechanism explains the different conformational preferences of the intermediate carbon-centered radicals, which is a crucial factor in the stereoselectivity of the reactions.

Framework structures of interconnected layers in calcium iron arsenides.

The new calcium iron arsenide compounds Ca(n(n+1)/2)(Fe(1-x)M(x))(2+3n)M'(n(n-1)/2)As((n+1)(n+2)/2) (n = 1-3; M = Nb, Pd, Pt; M' = □, Pd, Pt) were synthesized and their crystal structures determined by single-crystal X-ray diffraction. The series demonstrates the structural flexibility of iron arsenide materials, which otherwise prefer layered structures, as is known from the family of iron-based superconductors. In the new compounds, iron arsenide tetrahedral layers are bridged by iron-centered pyramids, giving rise to so far unknown frameworks of interconnected FeAs layers. Channels within the structures are occupied with calcium and palladium or platinum, respectively. Common basic building blocks are identified that lead to a better understanding of the building principles of these structures and their relation to CaFe4As3.

2D and 3D Self-Assembly of Fluorine-Free Pillar-[5]-Arenes and Perfluorinated Diacids at All-Aqueous Interfaces.

The interaction of perfluorinated molecules, also known as "forever chemicals" due to their pervasiveness, with their environment remains an important yet poorly understood topic. In this work, the self-assembly of perfluorinated molecules with multivalent hosts, pillar-[5]-arenes, is investigated. It is found that perfluoroalkyl diacids and pillar-[5]-arenes rapidly and strongly complex with each other at aqueous interfaces, forming solid interfacially templated films. Their complexation is shown to be driven primarily by fluorophilic aggregation and assisted by electrostatic interactions, as supported by the crystal structure of the complexes, and leads to the formation of quasi-2D phase-separated films. This self-assembly process can be further manipulated using aqueous two-phase system microdroplets, enabling the controlled formation of 3D micro-scaffolds.