Palladium-catalyzed cross coupling reaction of N-alkoxyimidoyl bromides and its application to one-pot synthesis of N-arylamines

The synthetic utility of N-alkoxyimidoyl halides is demonstrated using the palladium-catalyzed cross-coupling reaction. The Sonogashira and Suzuki-Miyaura coupling reactions of N-alkoxyimidoyl bromides produced versatile ketoxime ethers in good to excellent yields. A one-pot reaction of the imidoyl bromides with arylboronic acid and allylmagnesium bromide to produce N-arylamines via Suzuki-Miyaura coupling followed by domino reaction involving sequential addition-eliminative rearrangement-addition reactions was developed.     

A practical approach to non-natural or N-unsubstituted α-arylglycine derivatives: Hf(OTf)4-doped Me3SiCl system-catalyzed aminomethylation of electron-rich arenes with a new type of N,O-acetal

The authors have demonstrated the Hf(OTf)₄-doped Me₃SiCl system-catalyzed aminomethylation of electron-rich aromatic compounds, such as indoles and anilines, with new types of N,O-acetals having a variety of functional groups, such as cyano, ester, bis(trimethylsilyl)amino, diallylamino, and cyclic amino moieties, for the preparation of non-natural aromatic amino acid derivatives. Aminomethylation using an N,O-acetal with a bis(trimethylsilyl)amino group was particularly successful in the direct preparation of an N-unsubstituted α-indolylglycine derivative, which required only a standard aqueous workup.     

Two‐Step direct arylation for synthesis of naphthalenediimide‐based conjugated polymer

A naphthalenediimide (NDI)‐based conjugated polymer was synthesized by a two‐step direct C‐H arylation sequence. In the first step, two ethylenedioxythiophene units were coupled to NDI by direct arylation. In the second step, the direct arylation polycondensation of the monomer, formed in the first step, with 2,7‐dibromo‐9,9‐dioctylfluorene afforded the corresponding NDI‐based conjugated polymer ( PEDOTNDIF ) with molecular weight of 21,500 in 91% yield. The optical and electrochemical properties of the polymer were evaluated. The polymer showed ambipolar behavior in organic field‐effect transistors (OFETs). The electron mobility of PEDOTNDIF was estimated to be 2.3 × 10^?6 cm² V^?1 s^?1 using an OFET device with source‐drain (S‐D) Au electrodes. A modified OFET device with S‐D MgAg electrodes increased the electron mobility for PEDOTNDIF to 1.0 × 10^?5 cm² V^?1 s^?1 due to the more suitable work function of these electrodes, which reduced the injection barrier to the semiconducting polymer. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1401–1407     

Breath Figures of Nanoscale Bricks: A Universal Method for Creating Hierarchic Porous Materials from Inorganic Nanoparticles Stabilized with Mussel‐Inspired Copolymers

High‐performance catalysts and photovoltaics are required for building an environmentally sustainable society. Because catalytic and photovoltaic reactions occur at the interfaces between reactants and surfaces, the chemical, physical, and structural properties of interfaces have been the focus of much research. To improve the performance of these materials further, inorganic porous materials with hierarchic porous architectures have been fabricated. The breath figure technique allows preparing porous films by using water droplets as templates. In this study, a valuable preparation method for hierarchic porous inorganic materials is shown. Hierarchic porous materials are prepared from surface‐coated inorganic nanoparticles with amphiphilic copolymers having catechol moieties followed by sintering. Micron‐scale pores are prepared by using water droplets as templates, and nanoscale pores are formed between the nanoparticles. The fabrication method allows the preparation of hierarchic porous films from inorganic nanoparticles of various shapes and materials.

     

D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

The one‐step synthesis of D_3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η³‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η³‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.     

Adsorption and photochemical behaviors of the novel cationic xanthene derivative on the clay surface

Novel tetra-cationic xanthene derivative (Flu) was synthesized. Its adsorption and photochemical behaviors on the clay surface were investigated. Fluorescence quantum yield (?_f) and fluorescence lifetime were 0.50 and 2.9 ns for Flu/clay complex. ?_f of Flu was enough high (>0.1) even at high density conditions (0.080 molecules nm⁻²). It is supposed that the strong interaction between clay and Flu by the ‘Size-Matching Effect’ realizes the highly emissive clay complexes at high density adsorption condition by a suppression of a molecular aggregation, which tends to decrease the photochemical activity.     

Second-generation total synthesis of haterumalide NA using B-alkyl Suzuki-Miyaura coupling

Second-generation total synthesis of haterumalide NA, a potent cytotoxic marine macrolide, was achieved by using B-alkyl Suzuki-Miyaura coupling and Nozaki-Hiyama-Kishi coupling as key steps (1.2% in 33 steps). Compared to our first-generation approach, the second-generation synthesis is much improved in the yield of key intermediate.     

Synthesis of 4,5-fused tricyclic quinolines via an acid-promoted intramolecular Friedel–Crafts allenylation of aniline derivatives

A novel method for synthesizing 4,5-fused tricyclic quinoline derivatives based on an acid-promoted intramolecular Friedel–Crafts allenylation of anilines. Using aryl group-substituted propargyl alcohol derivatives with a meta-substituted N-Boc aniline unit as substrates, a four-step reaction sequence involving an acid-promoted intramolecular Friedel–Crafts allenylation of anilines, an acid-promoted intramolecular C–N bond formation, deprotection of the Boc group, and air oxidation proceeded in a single pot, producing the corresponding 4,5-fused tricyclic quinoline derivatives in 31–84% yield.     

High Diastereoselection of a Dissymmetric Capsule by Chiral Guest Complexation

Encapsulation of chiral guests in the dissymmetric capsule 1?4 BF₄ formed diastereomeric supramolecular complexes G ? 1?4 BF₄ ( G : guest). When chiral guests 2 a – q were encapsulated within the dissymmetric space of the self‐assembled capsule 1?4 BF₄, circular dichroism (CD) was observed at the absorption bands that are characteristic of the π–π* transition of the bipyridine moiety of the capsule, which suggests that the P and M helicities of the capsule are biased by the chiral guest complexation. The P helicity of diastereomeric complex (S)‐ 2 l ? 1?4 BF₄ was determined to be predominant, based on CD exciton coupling theory and DFT calculations. The diastereoselectivity was highly influenced by the ester substituents, such that benzyl ester moieties were good for improving the diastereoselectivity. A diastereomeric excess of 98 % was achieved upon the complexation of 2 j . The relative enthalpic and entropic components for the distereoselectivity were obtained from a van’t Hoff plot. The enthalpic components were linearly correlated with the substituent Hammett parameters (σ_p⁺). The electron‐rich benzyl ester moieties generated donor–acceptor π–π stacking interactions with the bipyridine moiety, which resulted in a significant difference in energy between the predominant and subordinate diastereomeric complexes.     

Palladium‐Catalyzed Direct Thiolation of Aryl CH Bonds with Disulfides

A catalytic variant of the direct thiolation of arenes, bearing directing groups, with disulfides or thiols has been developed under palladium and copper co‐catalysis. Both sulfenyl moieties of the disulfide could be incorporated into the thiolated products, therefore, the reactions reached completion with only half an equivalent of disulfide, with respect to the starting arene. Experimental evidence suggested that the reaction proceeds through a Pd^II/Pd^IV mechanism.