Stereospecific and asymmetric polymerization of 1-phenyldibenzosuberyl methacrylate with radical and anionic initiators

Stereospecific and asymmetric (helix-sense-selective) polymerization of 1-phenyldibenzosuberyl methacrylate (PDBSMA) was performed with radical and anionic initiators. A highly isotactic polymer having triad isotacticity greater than 97% was obtained by radical polymerization with (i-PrOCOO)₂ at 40°C. The radical polymerization of PDBSMA in (+)- and (-)-menthol gave (-)-and (+)-polymers, respectively, whose optical activity is ascribed to the prevailing one-handed helical conformation of a polymer chain. The radical copolymerization of PDBSMA with a small amount of an optically active monomer, (+)-phenyl-2-pyridyl-o-tolylmethyl methacrylate, afforded an optically active copolymer with the prevailing one-handed helical structure of PDBSMA sequences. Asymmetric anionic polymerization of PDBSMA was carried out with the complex of N, N′-diphenylethylenediamine monolithium amide and a chiral ligand, (+)-1-(2-pyrrolidinylmethyl)pyrrolidine in toluene at −78°C. The obtained polymer was highly isotactic and optically active due to nearly 100% one-handed helical structure.     

Transformation of Thia[7]helicene to Aza[7]helicenes and [7]Helicene-like Compounds via Aromatic Metamorphosis

[n]Helicenes with helically twisted structures have attracted increasing interest owing to their unique properties. Therefore, it has been an important issue to develop facile synthetic methodologies which allow access to a variety of [n]helicenes. Here we report the synthesis of [7]helicenes and [7]helicene-like compounds from the thia[7]helicene as a common starting material. Desulfurative dilithiation of the thia[7]helicene and the subsequent reaction with silicon and phosphorus electrophiles afforded the silole- and phosphole-fused [7]helicene-like compounds, respectively. The cyclopentadiene-fused [7]helicene-like compound and the pyrrole-fused aza[7]helicenes were also successfully synthesized via twofold S_NAr reactions of the thia[7]helicene S,S-dioxide with the carbon and nitrogen nucleophiles, respectively. The thia[7]helicene S,S-dioxide showed a slightly red-shifted absorption spectrum than the parent thia[7]helicene, which was well demonstrated by the theoretical calculations. The substituents on the silicon atom of silole-fused [7]helicene-like compounds have little impact on the longest absorption maximum. Such little effect of the substituents on absorption properties was also observed for cyclopentadiene-fused [7]helicene-like compounds and aza[7]helicenes and was well demonstrated by the theoretical calculations. The thia[7]helicene S,S-dioxide and the silole-fused [7]helicene-like compound exhibited bright blue emission, and the cyclopentadiene-fused [7]helicene-like compound and the aza[7]helicenes showed strong violet emission. Each single enantiomer of the aza[7]helicenes showed circularly-polarized luminescence with the dissymmetry factors of 4.2~4.4 × 10⁻³.     

Reactive-ion etch resistant polysulfones for microlithography

The various chemical approaches aimed at improving the reactive-ion etch resistance of poly(olefin sulfone)s are described. Resist systems based on incorporation of RIE-resistant moieties via random copolymerization, blending and block copolymer formation are described and lithographic properties noted.     

One‐Pot Synthetic Procedure for2,2′‐Disubstituted Biaryls via the Suzuki Coupling Reaction of Aryl Triflates in a Biphasic Solvent System

A one‐pot synthetic procedure for 2,2′‐disubstituted biaryls was developed via a Suzuki cross‐coupling reaction of aryl triflates in a biphasic solvent system. The effects of various bases and solvents were investigated. Results showed that the Na₂CO₃–toluene/H₂O combination gave the highest yields.     

Effects of Al concentration and resulting long-period superstructures on the plastic properties at room temperature of Al-rich TiAl single crystals

The role of Al₅Ti₃ and h-Al₂Ti long-period superstructures on the plastic properties of TiAl at room temperature is investigated on five single crystals with aluminium content comprised between 54.7 at.%, and 62.5 at.%. After annealing at 1200°C for 1?h, the Al₅Ti₃ superstructure develops in the L1₀ (γ) matrix upon increasing Al concentration except for Ti–62.5 at.%Al where h-Al₂Ti substitutes for Al₅Ti₃. The CRSS for <110]{111} first increases abruptly with the development of the Al₅Ti₃-type ordering. Then, the CRSS reaches a plateau at which dislocations assemble in groups of four to prevent extra anti-phase boundary (APB) from being engendered during glide throughout the Al₅Ti₃ phase. In Ti–62.5 at.%Al, the CRSS for ordinary slip further increases upon the precipitation of h-Al₂Ti in the L1₀ phase, whereas it decreases when the crystal is fully transformed into single-phased Al₅Ti₃. <101] superlattice dislocations are primarily activated under both the [210] and [1?1?8.6] load orientations irrespective of the Al concentration, but the dislocation microstructure strongly depends on orientation as well as on the degree of Al₅Ti₃ ordering. In the [210] orientation, the frequency of the decomposition of <101] dislocations into 1/2<110] and 1/2<112] dislocations decreases abruptly with the development of Al₅Ti₃. This is interpreted in terms of the increased difficulty to move ordinary dislocations. Under the [1?1?8.6] orientation, the density of faulted dipoles diminishes remarkably with the development of Al₅Ti₃. This is consistent with the transformation of the low energy extrinsic stacking fault of the L1₀ phase into a higher energy complex extrinsic stacking fault.     

Multinuclear cobalt–salen complexes with phenylene linker for epoxide polymerizations

Di‐ and trinuclear cobalt (Co)–salen complexes with a benzene ring as a rigid linker were explored for epoxide polymerizations. The dinuclear Co–salen complex with a 1,2‐phenylene linker showed higher catalytic activity than the dinuclear Co–salen complex with a 1,3‐phenylene linker and the trinuclear Co–salen complex with a 1,3,5‐benzenetriyl linker for the copolymerization of propylene oxide (PO) with carbon dioxide. A combination of the absolute configuration of the two Co–salen moieties was found to affect its catalytic activity. The optimized dinuclear Co–salen complex with a heterochiral combination demonstrated highest activity and maintained its catalytic activity under a low catalyst concentration. The heterochiral dinuclear Co–salen complex also showed high activity for the copolymerization of PO with cyclic anhydride. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2150–2159     

Simple Synthesis of a Heterocyclophane Exhibiting Anti-c-Met Activity by Acting as a Hatch Blocking Access to the Active Site**

A simple approach to the synthesis of heterocyclophane consisting of two 4,4’-bithiazoles has been developed in mild conditions. The heterocyclophane with two short chains was conveniently prepared by Hantzsch thiazoles synthesis using the reaction of 3-tert-butoxycarbonyl-3-azapentanethiocarboxamide with 1,4-dibromobutane-2,3-dione in methanol under reflux for only 15 min. Amino groups at the linkers of this heterocyclophane can be functionalized to give acylated and carbamate derivatives. Their properties as protein kinase inhibitors were investigated, and one of the heterocyclophanes exhibited specific anti-activity for c-mesenchymal epithelial transition factor (IC₅₀=603 nm ), among seven types of protein kinases investigated. The computational site identification by ligand competitive saturation method was used to determine why the one heterocyclophane exhibited strong anti-activity for c-mesenchymal epithelial transition factor.     

Representation type of Hecke algebras of type

In this paper we provide a complete classification of the representation type for the blocks for the Hecke algebra of type , stated in terms of combinatorical data. The computation of the complexity of Young modules is a key component in the proof of this classification result.