Grafting of Polymers onto a Crosslinked Polymer Carrying Carboxyl Groups as a Model Compound for Carbon Black

Abstract

A cation-exchange resin (a crosslinked polymer carrying carboxyl groups) was used as a model compound for carbon black, and the grafting of several polymers to the resin was investigated. Reaction of acyl chloride groups that had been placed on the ion-exchange resin with polymers having hydroxyl or amino groups, such as polypropylene glycol, polyethylene glycol, polybutadiene glycol, polyvinyl alcohol, silicone diol, silicone diamine, and polyethyleneimine, resulted in grafting to the ion-exchange resin. In further experiments, primary amino groups were placed on the cation-exchange resin by reaction of acyl chloride groups with ethylenediamine. It was found that ring-opening polymerization of γmethyl L-glutamate N-carboxyanhydride is initiated by the amino groups on the resin, and polypeptide was grafted from the cation-exchange resin. Therefore, the reactivity of carboxyl groups on the resin was found to be similar to that on carbon black. However, carboxyl groups on the resin failed to initiate the cationic polymerization of vinyl monomers, in contrast to those on carbon black. This suggested that the acidity of carboxyl groups on carbon black is greater than on the cation-exchange resin.     

Water,an Essential Element for a ZnII‐Catalyzed Asymmetric Quinone Diels‐Alder Reaction: Multi‐Selective Construction of Highly Functionalized cis‐Decalins

A Zn^II complex of a C₂‐chiral bisamidine‐type sp²N bidentate ligand ( L _R ) possessing two dioxolane rings at both ends catalyzes a highly efficient quinone asymmetric Diels‐Alder reaction (qADA) between o‐alkoxy‐p‐benzoquinones and 1‐alkoxy‐1,3‐butadienes to construct highly functionalized chiral cis‐decalins, proceeding in up to a >99:1 enantiomer ratio with a high generality in the presence of H₂O (H₂O:Zn^II=4–6:1). In the absence of water, little reaction occurs. The loading amount of the chiral ligand can be minimized to 0.02 mol % with a higher Zn/ L _R ratio. This first success is ascribed to a supramolecular 3D arrangement of substrates, in which two protons of an “H₂O‐Zn^II” reactive species make a linear hydrogen bond network with a dioxolane oxygen atom and one‐point‐binding diene; the Zn^II atom captures the electron‐accepting two‐points‐binding quinone fixed on the other dioxolane oxygen atom via an n‐π* attractive interaction. The mechanisms has been supported by ¹H NMR study, kinetics, X‐ray crystallographic analyses of the related Zn L _R complexes, and ligand and substrate structure‐reactivity‐selectivity relationship.     

Chiral Vinyl Sulfoxides as Useful Reagents for the Synthesis of β-Amino Acid Derivatives

(S)- and (R)-β-amino acid derivatives were synthesized by the asymmetric conjugate addition of ammonia and piperidazine to t-butyl (E)-2-[(R)- and (S)-p-tolylsulfinyl]cinnamates, respectively.     

Effect of the sputtering parameters on the physical properties and photocatalytic reactivity of TiO2 thin films prepared by an RF magnetron sputtering deposition method

Visible light-responsive TiO₂ (Vis-TiO₂) thin films were successfully developed by applying a radio-frequency magnetron sputtering deposition method by controlling various sputtering parameters such as the substrate temperature, Ar gas pressure, and the target-to-substrate distance. UV–Vis, XRD and SEM investigations revealed that optical property, the crystal structure, and photocatalytic activity of Vis-TiO₂ are strongly affected by the sputtering parameters during the deposition step. Vis-TiO₂ was found to act as an efficient photocatalyst for the H₂ and O₂ evolution from water under visible light irradiation (λ ≥ 420 nm). SIMS investigations have revealed that a slight decrease in the O/Ti ratio of the TiO₂ thin films plays an important role in the modification of the electronic properties of Vis-TiO₂ thin films, enabling them to absorb visible light.     

Structure Determination and Total Synthesis of (+)‐16‐Hydroxy‐16,22‐dihydroapparicine

Herein, we describe the first asymmetric total synthesis and determination of the relative and absolute stereochemistry of naturally occurring 16‐hydroxy‐16,22‐dihydroapparicine. The key steps include 1) a novel phosphinimine‐mediated cascade reaction to construct the unique 1‐azabicyclo[4.2.2]decane core, including a pseudo‐aminal‐type moiety; 2) a highly stereospecific 1,2‐addition of 2‐acylindole or a methylketone through a Felkin–Anh transition state for the construction of a tetrasubstituted carbon center; and 3) an intramolecular chirality‐transferring Michael reaction of the ketoester, with neighboring‐group participation, to introduce a chiral center at C15 in the target molecule. In addition, we evaluated the antimalarial activity of synthetic (+)‐(15S,16R)‐16‐hydroxy‐16,22‐dihydroapparicine and its intermediate against chloroquine‐resistant Plasmodium falciparum (K1 strain) parasites.     

Copper‐Catalyzed Reaction of Trifluoromethylketones with Aldehydes via a Copper Difluoroenolate

A copper‐catalyzed reaction of easily accessible α,α,α‐trifluoromethylketones with various aldehydes affords difluoro‐methylene compounds in the presence of diboron and NaOtBu. The key process of the reaction is the formation of a copper difluoroenolate by 1,2‐addition of a borylcopper intermediate to α,α,α‐trifluoromethylketones and subsequent β‐fluoride elimination. Mechanistic studies including the isolation and characterization of a possible anionic copper alkoxide intermediate are also described.     

Rapid Synthesis of D‐A′‐π‐A Dyes through a One‐Pot Three‐Component Suzuki–Miyaura Coupling and an Evaluation of their Photovoltaic Properties for Use in Dye‐Sensitized Solar Cells

Twenty‐four D‐A′–π‐A dyes were rapidly synthesized through a one‐pot three‐component Suzuki–Miyaura coupling reaction, which was assisted by microwave irradiation. We measured the absorption spectra, electrochemical properties, and solar‐cell performance of all the synthesized dyes. The D5 πA4 dye contained our originally designed rigid and nonplanar donor and exerted the highest efficiency at 5.4 %. The short‐circuit current (J_sc) was the most important parameter for the conversion efficiency (η) in the case of the organic D‐A′‐π‐A dyes. Optimal ranges for the D‐A′‐π‐A dyes were observed for high values of J_sc/λ_max at λ=560–620 nm, an optical‐absorption edge of λ=690–790 nm, and E_HOMO and E_LUMO values of <1.14 and ?0.56 to ?0.76 V, respectively.     

Enantioselective Total Synthesis of (+)‐Neostenine

A chirality transfer approach using acyclic polyol intermediates for the synthesis of (+)‐neostenine ( 1 ) has been developed. The sequential Overman/Claisen rearrangement of an allylic 1,2‐diol was especially useful, installing two contiguous stereocenters with complete diastereoselectivity in a one‐pot sequence. The SmI₂‐mediated cyclization and the subsequent chemoselective reduction of a lactam moiety accomplished the first enantioselective total synthesis of (+)‐neostenine ( 1 ).