Unexpected formation of a co-crystal containing the chalcone ()-1-(5-chloro-thio-phen-2-yl)-3-(3-methyl-thio-phen-2-yl)prop-2-en-1-one and the keto-enol tautomer ()-1-(5-chloro-thio-phen-2-yl)-3-(3-methyl-thio-phen-2-yl)prop-1-en-1-ol.

The title crystal structure is assembled from the superposition of two mol-ecular structures, ()-1-(5-chloro-thio-phen-2-yl)-3-(3-methyl-thio-phen-2-yl)prop-2-en-1-one, CHClOS (93%), and ()-1-(5-chloro-thio-phen-2-yl)-3-(3-methyl-thio-phen-2-yl)prop-1-en-1-ol, CHClOS (7%), 0.93CHClOS·0.07CHClOS.

Synthesis, characterization, crystal structure and supra-molecularity of ethyl ()-2-cyano-3-(3-methyl-thio-phen-2-yl)acrylate and a new polymorph of ethyl ()-2-cyano-3-(thio-phen-2-yl)acrylate.

The synthesis, crystal structure and structural motif of two thio-phene-based cyano-acrylate derivatives, namely, ethyl ()-2-cyano-3-(3-methyl-thio-phen-2-yl)acrylate (), CHNOS, and ethyl ()-2-cyano-3-(thio-phen-2-yl)acrylate (), CHNOS, are reported. Derivative crystallized with two independent molecules in the asymmetric unit, and derivative represents a new monoclinic (2/) polymorph. The mol-ecular conformations of and the two polymorphs of are very similar, as all non-H atoms are planar except for the methyl of the ethyl groups.

Synthesis of β-Substituted γ-Aminobutyric Acid Derivatives through Enantioselective Photoredox Catalysis.

β-Substituted chiral γ-aminobutyric acids feature important biological activities and are valuable intermediates for the synthesis of pharmaceuticals. Herein, an efficient catalytic enantioselective approach for the synthesis of β-substituted γ-aminobutyric acid derivatives through visible-light-induced photocatalyst-free asymmetric radical conjugate additions is reported. Various β-substituted γ-aminobutyric acid analogues, including previously inaccessible derivatives containing fluorinated quaternary stereocenters, were obtained in good yields (42-89 %) and with excellent enantioselectivity (90-97 % ee).

Synthesis of Fluorescent 1-(3-Amino-4-(4-(tert-butyl)phenyl)-6-(p-tolyl)furo[2,3-b]pyridin-2-yl)ethan-1-one: Crystal Structure, Fluorescence Behavior, Antimicrobial and Antioxidant Studies.

Furopyridine III, namely 1-(3-amino-4-(4-(tert-butyl)phenyl)-6-(p-tolyl)furo[2,3-b]pyridin-2-yl)ethan-1-one, synthesized from 4-(4-(tert-butyl)phenyl)-2-oxo-6-(p-tolyl)-1,2-dihydropyridine-3-carbonitrile I in two steps. The title compound is characterized by NMR, MS and its X-ray structure. The molecular structure consists of planar furopyridine ring with both phenyl rings being inclined from the furopyridine scaffold to a significant different extent.

Octahedral Ruthenium Complex with Exclusive Metal-Centered Chirality for Highly Effective Asymmetric Catalysis.

A novel ruthenium catalyst is introduced which contains solely achiral ligands and acquires its chirality entirely from octahedral centrochirality. The configurationally stable catalyst is demonstrated to catalyze the alkynylation of trifluoromethyl ketones with very high enantioselectivity (up to >99% ee) at low catalyst loadings (down to 0.2 mol%).

A Rhodium Catalyst Superior to Iridium Congeners for Enantioselective Radical Amination Activated by Visible Light.

A bis-cyclometalated rhodium(III) complex catalyzes a visible-light-activated enantioselective α-amination of 2-acyl imidazoles with up to 99 % yield and 98 % ee. The rhodium catalyst is ascribed a dual function as a chiral Lewis acid and, simultaneously, as a light-activated smart initiator of a radical-chain process through intermediate aminyl radicals. Notably, related iridium-based photoredox catalysts reported before were unsuccessful in this enantioselective radical C-N bond formation.

Improved δ-valerolactam templates for the assembly of Aβ-miniamyloids by boronic ester formation.

The 6,7,8,8a-cis (all-cis) substituted δ-valerolactams of type 10, 11 and 12 are high-affinity diols for boronic ester formation, superior to the corresponding 6,7-trans analogues 1, 3 and 4. X-ray and NMR structure analysis have identified the differences of the six-membered ring conformations which cause the improved esterification properties of the all-cis stereoisomers. The homooligomeric all-cisδ-valerolactams 46-48 are used as polyol templates for the self-assembly of peptidic oligomers 49-52 by dynamic covalent chemistry.

Regioselective Ring-Opening Polymerization of a Polyhydroxycarboxylic Acid for the Synthesis of a Nanoscale Carrier Material with pH-Dependent Stability and Sustained Drug Release.

Synthetic polyesters are usually composed of monohydroxycarboxylic acids to avoid the problem of regioselectivity during ring-opening polymerization. In contrast, the linear polyester BICpoly contains four secondary OH groups and is nevertheless esterified regioselectively at only one of these positions. Neither the synthesis of the tricyclic monomers nor the ring-opening polymerization requires protecting groups, making BICpoly an attractive novel and biocompatible polymer.

Asymmetric photoredox transition-metal catalysis activated by visible light.

Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest.

(S,2S,3S)-2-(2-Methyl-propan-2-sulfin-amido)-3-phenyl-butyronitrile.

The absolute configuration has been determined for the title compound, C(14)H(20)N(2)OS. There are two independent mol-ecules in the asymmetric unit. Inter-molecular N-H⋯O hydrogen bonds are observed in the crystal packing, forming infinite chains with the base vectors [100] and [010].

(S,2S,3R)-2-(2-Methyl-propane-2-sulfin-amido)-3-phenyl-butyronitrile.

The absolute configuration has been determined for the title compound, C(14)H(20)N(2)OS. Inter-molecular N-H⋯O hydrogen bonds are observed in the crystal packing, forming infinitive one-dimensional chains with the base vector [100].

[(Ph) (NMe )C(OLi)⋅THF] : Crystal Structure of the Tetrahedral Intermediate Formed in the Reaction of N,N-Dimethylbenzamide and Phenyllithium.

Information on the reaction path for the 1,2-eliminiation of LiNMe to form benzophenone is provided by the X-ray crystal structure analysis of the tetrahedral adduct [(Ph) (NMe )C(OLi)⋅THF] (a portion of the structure is shown schematically), which is prepared from N,N-dimethylbenzamide and phenyllithium. A N1-Li1 interaction, which is not observed, would lead to loss of the anomeric effect (n →σ ) as well as high conformational strain along the C1-N1 bond.

The Crystal Structures of a Lower Order and a "Higher Order" Cyanocuprate: [tBuCu(CN)Li(OEt ) ] and [tBuCutBu{Li(thf)(pmdeta)} CN].

Different types of bonding are present in cyanocuprates 1 and 2, whose crystal structures could be determined (the drawings below show the important structural characteristics). Accordingly, 1 is a lower order cyanocuprate of the type RCu(CN)Li, whereas 2, which is of the type R Cu(CN)Li , does not exist as a "higher order" cyanocuprate with Cu-CN bonds, but rather as a cyano-Gilman cuprate.

[Lithium tert-butylperoxide] : Crystal Structure of an Aggregated Oxenoid.

The X-ray crystal structure of the dodecameric lithium tert-butylperoxide [2] is the first of an alkali or alkaline earth peroxide. It shows the lithium ion bridging the two oxygen atoms of the peroxide unit and a slight lenghtening of the O-O bond, in agreement with quantum-chemical calculations. A calculation for the model reaction of MeLi with LiOOH to give MeOLi and LiOH reveals the importance of Li bridging the O-O bond in the transition state of this reaction, as similarly discussed for many oxidation reactions of (transition-) metal peroxides.