Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage

Various aryl‐, alkenyl‐, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross‐coupled products, catalyzed by commercially available [Ni(cod)₂] (cod=1,5‐cyclooctadiene) catalysts with N‐heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh₃)₂Cl₂] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot.     

Synthesis of All Stereoisomers of Monomeric Spectomycin A1/A2 and Evaluation of Their Protein SUMOylation-Inhibitory Activity

A synthetic methodology to access all possible stereoisomers of spectomycin A1 (SMA1) and A2 (SMA2) has been established through late-stage diversification. The key reaction for the construction of all four diastereomers is an intramolecular cyclization based on the umpolung of π-allyl palladium species with bis(pinacolato)diborane (B₂(pin)₂). Silyl group assisted direct benzylic oxidation of each isomer enabled construction of the fragile β-hydroxytetralone skeleton to provide the SMAs. The relative and absolute stereochemistry of SMA2 was also determined, and the absolute stereochemistry of SMA1 was extrapolated based on the optical rotation of SMA2. The axial chirality of SMAs is discussed based on circular dichroism spectra and DFT calculations, and it is concluded that the M isomer is predominant in solution. Biochemical assessment of all isomers in vitro revealed that the C9 hydroxyl group and dimeric structure were both important for protein SUMOylation-inhibitory activity.     

Effects of graded porous structure on local strain distribution under compression in silicone rubber

Silicone rubber samples with gradually changing pore sizes within the range of 70–610 μm are produced using an improved spacer method. The samples are scanned using an X‐ray computed tomography to evaluate their graded structure as compared to uniform rubber. A compressive test reveals that graded porous silicone rubber has characteristic stress–strain curves whose slope changes within a specific strain range depending on the porous structure. Analysis results of local strain based on a digital image correlation of the graded porous silicone rubber under compression demonstrate that the characteristic stress–strain properties are caused by shifts in the main deformation region in the graded structure. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1033–1042     

Unexpected formation of benziphthalocyanine dimer: An easily synthesizable dimer of phthalocyanine analogue

Methylene-bridged benziphthalocyanine dimer 2 was unexpectedly generated by the reaction of dihydroxybenziphthalocyanine 1 and formaldehyde in the presence of a catalytic amount of a base at room temperature. Single-crystal X-ray diffraction analysis of 2 revealed a V-shaped structure. Dimer 2 exhibited longer-wavelength absorption and fluorescence bands than monomer 1 in the near-IR region.     

Characterization of posticlure and the structure-related sex pheromone candidates prepared by epoxidation of (6Z,9Z,11E)-6,9,11-trienes and (3Z,6Z,9Z,11E)-3,6,9,11-tetraenes

trans-11,12-Epoxy-(6Z,9Z)-6,9-henicosadiene (posticlure) has been identified from a pheromone gland of the lymantriid species, Orgyia postica. Since the diversity of Lepidoptera suggests that some species utilize the structure-related epoxy compound as a sex pheromone component, epoxydienes and epoxytrienes derived from (6Z,9Z,11E)-6,9,11-trienes and (3Z,6Z,9Z,11E)-3,6,9,11-tetraenes with a C₁₉–C₂₁ chain were systematically synthesized and the chemical data were accumulated in order to contribute to a new pheromone research. Peracid oxidation of each triene and each tetraene produced, respectively, a mixture of three epoxydienes (cis-6,7-epoxy-9,11-diene; cis-9,10-epoxy-6,11-diene; and trans-11,12-epoxy-6,9-diene) and four epoxytrienes (cis-3,4-epoxy-6,9,11-triene; cis-6,7-epoxy-3,9,11-triene; cis-9,10-epoxy-3,6,11-triene; and trans-11,12-epoxy-3,6,9-triene). While the 9,10-epoxy compounds were unstable and, interestingly, converted into 9-ketone derivatives after chromatography over SiO₂, each positional isomer was isolated by HPLC equipped with an ODS column, and the chemical structure was determined by NMR analysis. On the GC-MS analysis with a DB-23 column, the positional isomers were also eluted separately and characteristic mass spectra were proposed. By comparing the spectral data of the epoxy compounds with a different carbon chain, diagnostic fragment ions reflecting the chemical structure were determined as follows: m/z 79, 109, 113, and M-114 for the 6,7-epoxydienes; m/z 69, 97, 111, 139, and M-111 for the 9,10-epoxydienes; m/z 57, 79, 109, 136, M-151, and M-111 for the 11,12-epoxydienes; m/z 79, 91, 105, and 119 for the 3,4-epoxytrienes; m/z 79, 124, M-124, M-96, and M-69 for the 6,7-epoxytrienes; m/z 79, 95, 109, 137, and M-108 for the 9,10-epoxytrienes; and m/z 79, 134, M-149, M-109, and M-95 for the 11,12-epoxytrienes.     

Chirality Induction by Formation of Assembled Structures Based on Anion‐Responsive π‐Conjugated Molecules

Anion‐responsive π‐conjugated compounds having chiral alkyl chains were synthesized. Circular dichroism (CD) and circularly polarized luminescence (CPL) were observed in the solution‐state assemblies of the chiral anion receptors and those of their anion complexes as salts of a planar triazatriangulenium cation. The CD and CPL spectral patterns of the ion‐pair‐based assemblies were completely opposite to those of the anion‐free assemblies, and this suggests that anion binding and subsequent ion pairing change the chirality of the assembly modes.     

Preparation of multiwall carbon nanotubes (MWCNTs) stabilised by highly branched hydrocarbon surfactants and dispersed in natural rubber latex nanocomposites

The performance of single-, double- and triple-chain anionic sulphosuccinate surfactants for dispersing multiwall carbon nanotubes (MWNCTs) in natural rubber latex (NR-latex) was studied using a range of techniques, including field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Raman spectroscopy. The conductivities of the nanocomposites were also investigated using four-point probe measurements. Here, MWCNTs were efficiently dispersed in NR-latex with the aid of hyperbranched tri-chain sulphosuccinate anionic surfactants, specifically sodium 1,4-bis(neopentyloxy)-3-(neopentyloxycarbonyl)-1,4-dioxobutane-2-sulphonate (TC14). This paper highlights that TC14 performs much better than that of the commercially available surfactant sodium dodecyl sulphate (SDS), demonstrating how careful consideration of surfactant architecture leads to improved dispersibility of MWCNTs in NR-latex. The results should be of significant interest for improving nanowiring applications suitable for aerospace-based technology.     

Sila- and Germacarboxylic Acids: Precursors for the Corresponding Silyl and Germyl Radicals

Silicon-containing compounds are widely used as synthetic building blocks, functional materials, and bioactive reagents. In particular, silyl radicals are important intermediates for the synthesis and transformation of organosilicon compounds. Herein, we describe the first protocol for the generation of silyl radicals by photoinduced decarboxylation of silacarboxylic acids, which can be easily prepared in high yield on a gram scale and are very stable to air and moisture. Irradiation of silacarboxylic acids with blue LEDs (455 nm) in the presence of a commercially available photocatalyst releases silyl radicals, which can further react with various alkenes to give the corresponding silylated products in good-to-high yields with broad functional-group compatibility. This reaction proceeds in the presence of water, enabling efficient deuterosilylation of alkenes with D₂O as the deuterium source. Germyl radicals were similarly obtained.     

Rhodium-Catalyzed Highly Diastereo- and Enantioselective Synthesis of a Configurationally Stable S-Shaped Double Helicene-Like Molecule

An S-shaped double helicene-like molecule (>99 % ee), possessing stable helical chirality, has been synthesized by the rhodium(I)/difluorphos complex-catalyzed highly diastereo- and enantioselective intramolecular double [2+2+2] cycloaddition of a 2-naphthol- and benzene-linked hexayne. The collision between two terminal naphthalene rings destabilizes the helical chirality of the S-shaped double helicene-like molecule, but the introduction of two additional fused benzene rings significantly increases the configurational stability. Thus, no epimerization and racemization were observed even at 100 °C. The enantiopure S-shaped double helicene-like molecule forms a trimer through the multiple C−H⋅⋅⋅π and C−H⋅⋅⋅O interactions in the solid-state. The trimers stack to form columnar packing structures, in which neighboring stacks have opposite dipole directions. The accumulation of helical structures in the same direction in the S-shaped double helicene-like molecule enhanced the chiroptical properties.