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The rates of reactions of 5-dimethylamino-1-naphthalenesulphonyl chloride (dansyl chloride) with butylamine in organic solvents have been measured in the presence of polymer such as polyoxyethylene (POE) or polystyrene (PS) as cosolvent and compared with those in the presence of cosolvents of low molecular weight analogues, viz. diethyloxyethane (DEE) and toluene (Tol.). Acceleration by cosolvent POE, compared with DEE, increases with increasing volume fraction of cosolvent and the effect depends on the degree of polymerization of the polymer cosolvent. Similarly, addition of cosolvent PS to ethyl acetate or chloroform results in increase in the reaction rate as compared with cosolvent Tol. The effect by PS also showed dependence on the degree of polymerization. The effect of polymer cosolvent on chemical reactions between two low molecular weight species is explained in terms of the thermodynamics of polymer solutions. 相似文献
33.
Defect turbulence described by the one-dimensional complex Ginzburg–Landau equation is investigated and analyzed via a birth–death process of the local structures composed of defects, holes, and modulated amplitude waves (MAWs). All the number statistics of each local structure, in its stationary state, are subjected to Poisson statistics. In addition, the probability density functions of interarrival times of defects, lifetimes of holes, and MAWs show the existence of long-memory and some characteristic time scales caused by zigzag motions of oscillating traveling holes. The corresponding stochastic process for these observations is fully described by a non-Markovian master equation. 相似文献
34.
Dr. Jing Li Dr. Martin J. Lear Prof. Yujiro Hayashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(19):5901-5905
Cyclopropanes are traditionally prepared by the formal [2+1] addition of carbene or radical based C1 units to alkenes. In contrast, the one-pot intermolecular cyclopropanation of alkanes by redox active C1 units has remained unrealised. Herein, we achieved this process simply by exposing β-aryl propionitriles and C1 radical precursors (N-oxy esters) to base and blue light. The overall process is redox-neutral and a photocatalyst, whether metal- or organic-based, is not required. Our findings support that single electron transfer (SET) from the α-cyano carbanion of the propionitrile to the N-oxy ester is facilitated by blue-light via their electron donor–acceptor (EDA) complex. The α-cyano carbon radical thus formed can then lose a β-proton to form a π-resonance stabilised radical anion that preferentially couples at the benzylic β-position with a decarboxylated C1 radical unit. This new transition metal-free chemistry tolerates both electron rich and electron deficient (hetero)aryl systems, even sulfide or alkene functionality, to afford a range of cis-aryl/cyano cyclopropanes bearing congested tetrasubstituted quaternary carbons. 相似文献
35.
Kyoichi Hanada Juntaro Nogami Prof. Dr. Kazunori Miyamoto Norihiko Hayase Dr. Yuki Nagashima Yusuke Tanaka Dr. Atsuya Muranaka Prof. Dr. Masanobu Uchiyama Prof. Dr. Ken Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(36):9313-9319
The enantioselective synthesis of aza[6] and [7]helicene-like molecules have been achieved by the cationic rhodium(I)/axially chiral biaryl bisphosphine complex-catalyzed intramolecular [2+2+2] cycloaddition of cyanodiynes. This protocol was successfully applied to the diastereo- and enantioselective synthesis of an S-shaped double aza[6]helicene-like molecule with a high ee value of 89 %. Although no epimerization and racemization were observed in the double carbo[6]helicene-like molecule at 80 °C, epimerization and racemization of the double aza[6]helicene-like molecule proceeded at 80 °C. This double aza[6]helicene-like molecule showed good fluorescent quantum yields and chiroptical responses under both neutral and acidic conditions. 相似文献
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Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage
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Ze‐Kun Yang Dong‐Yu Wang Hiroki Minami Hiroyuki Ogawa Takashi Ozaki Dr. Tatsuo Saito Dr. Kazunori Miyamoto Dr. Chao Wang Prof. Dr. Masanobu Uchiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15693-15699
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. 相似文献
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Dr. Yusaku Nomura Dr. Frédéric Thuaud Dr. Daisuke Sekine Prof. Dr. Akihiro Ito Satoko Maeda Dr. Hiroyuki Koshino Dr. Daisuke Hashizume Dr. Atsuya Muranaka Dr. Thomas Cruchter Prof. Dr. Masanobu Uchiyama Prof. Dr. Satoshi Ichikawa Prof. Dr. Akira Matsuda Prof. Dr. Minoru Yoshida Prof. Dr. Go Hirai Prof. Dr. Mikiko Sodeoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8387-8392
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. 相似文献