Synthesis of Dibenzo[c,e]oxepin‐5(7H)‐ones from Benzyl Thioethers and Carboxylic Acids: Rhodium‐Catalyzed Double C?H Activation Controlled by Different Directing Groups

A rhodium(III)‐catalyzed cross‐coupling of benzyl thioethers and aryl carboxylic acids through the two directing groups is reported. Useful structures with diverse substituents were efficiently synthesized in one step with the cleavage of four bonds (C H, C S, O H) and the formation of two bonds (C C, C O). The formed structure is the privileged core in natural products and bioactive molecules. This work highlights the power of using two different directing groups to enhance the selectivity of a double C H activation, the first of such examples in cross‐oxidative coupling.     

Synthesis of Indolophanes by Photochemical Macrocyclization

Herein, we report the synthetically practical, short, and general access to novel indolophane architectures by means of a photochemical C?H activation process—the Witkop cyclization. These highly strained scaffolds were obtained by photoinduced ring closure and feature atropisomerism as well as aromatic ring current effects, which both have been investigated. The prevailing regioselectivity of theWitkop cyclization reaction was completely reversed by the presence of a quaternary carbon center, exerting a strong Thorpe–Ingold effect on the system for which experimental‐evidence is provided.     

Visible‐Light‐Induced Trifluoromethylation of Isonitrile‐Substituted Methylenecyclopropanes: Facile Access to 6‐(Trifluoromethyl)‐7,8‐Dihydrobenzo[k]phenanthridine Derivatives

A new visible‐light‐induced trifluoromethylation of isonitrile‐substituted methylenecyclopropanes is developed. A range of substituted 6‐(trifluoromethyl)‐7,8‐dihydrobenzo[k]phenanthridine derivatives are readily furnished by this newly developed tandem reaction with moderate to good yields. This reaction allows the direct formation of two six‐membered rings and three new C?C bonds, including the C?CF₃ bond, under visible light irradiation.     

Freezing the Dynamic Gap for Selectivity: Motion‐Based Design of Inhibitors of the Shikimate Kinase Enzyme

Shikimate kinase (SK), the fifth enzyme of the aromatic amino acid biosynthesis, is a recognized target for antibiotic drug discovery. The potential of the distinct dynamic apolar gap, which isolates the natural substrate from the solvent environment for catalysis, and the motion of Mycobacterium tuberculosis and Helicobacter pylori SK enzymes, which was observed by molecular dynamics simulations, was explored for inhibition selectivity. The results of the biochemical and computational studies reveal that the incorporation of bulky groups at position C5 of 5‐aminoshikimic acid and the natural substrate enhances the selectivity for the H. pylori enzyme due to key motion differences in the shikimic acid binding domain (mainly helix α5). These studies show that the less‐exploited motion‐based design approach not only is an alternative strategy for the development of competitive inhibitors, but could also be a way to achieve selectivity against a particular enzyme among its homologues.     

New Perspectives for Old Clusters: Anderson–Evans Anions as Building Blocks of Large Polyoxometalate Frameworks in a Series of Heterometallic 3 d–4 f Species

A series of nine [Sb₇W₃₆O₁₃₃Ln₃M₂(OAc)(H₂O)₈]^17? heterometallic anions ( Ln₃M₂ ; Ln=La–Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs‐type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW₉O₃₃} capping unit formed by a planar {MW₆O₂₄} fragment to which three {WO₂} groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the ?‐Keggin cluster. It is shown, for the first time, that classical Anderson–Evans {MW₆O₂₄} anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk‐shaped species is also revealed. The Ln₃M₂ anions possess chirality owing to a {Sb₄O₄} cluster being encapsulated in left‐ or right‐handed orientations. Their ability to self‐associate in blackberry‐type vesicles in solution has been assessed for the Ce₃Co₂ derivative.     

Thermal Decomposition Kinetics of Ginkgo biloba Leaves Polyprenol in Nitrogen Atmosphere

The nonisothermal decomposition kinetics of Ginkgo biloba leaves polyprenol (GBP) and cleaved situation of its chemical bond during thermal decomposition process were first investigated using thermogravimetric (TG) and TG‐FTIR technology. The results of thermal decomposition kinetics revealed that the nonisothermal decomposition mechanism of GBP corresponds to first‐order chemical reaction with n = 1, integral form g(a) = –ln(1 – a) and differential form f(a) = 1 – a. TG‐FTIR results demonstrated that absorbance of –CH₃, unsaturated C–H bond, =CH₂, accumulated C=C, –OH, and so on constantly increased with thermal decomposition reaction went on. In addition, storage life of GBP was also evaluated. These data could provide theoretical guidance for purification under high temperature and other thermal application of GBP.     

NMR studies on 4‐thio‐5‐furan‐modified and 4‐thio‐5‐thiophene‐modified nucleosides

Systematic NMR characterization of 4‐thio‐5‐furan‐pyrimidine nucleosides or 4‐thio‐5‐thiophene‐pyrimidine nucleosides (ribonucleosides and 2′‐deoxynucleosides) was performed. All proton and carbon signals of 4‐thio‐5‐thiophene‐ribouridine and related analogues were unambiguously assigned. The orientations of the base (4‐thiouridine or its deoxy analogue) relative to the ring (furan or thiophene) are explored by a NMR approach and further supported by X‐ray crystallographic studies. The procedures presented here would be applicable to other modified nucleosides and nucleotides. Copyright © 2016 John Wiley & Sons, Ltd.     

Copper Causes Regiospecific Formation of C4F8‐Containing Six‐Membered Rings and their Defluorination/Aromatization to C4F4‐Containing Rings in Triphenylene/1,4‐C4F8I2 Reactions

The presence of Cu in reactions of triphenylene (TRPH) and 1,4‐C₄F₈I₂ at 360 °C led to regiospecific substitution of TRPH ortho C(β) atoms to form C₄F₈‐containing rings, completely suppressing substitution on C(α) atoms. In addition, Cu caused selective reductive‐defluorination/aromatization (RD/A) to form C₄F₄‐containing aromatic rings. Without Cu, the reactions of TRPH and 1,4‐C₄F₈I₂ were not regiospecific and no RD/A was observed. These results, supported by DFT calculations, are the first examples of Cu‐promoted 1) regiospecific perfluoroannulation, 2) preparative C?F activation, and 3) RD/A. HPLC‐purified products were characterized by X‐ray diffraction, low‐temperature PES, and ¹H/¹⁹F NMR.