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931.
Dr. Oleg A. Levitskiy Olga I. Aglamazova Prof. Dr. Vadim A. Soloshonok Dr. Hiroki Moriwaki Prof. Dr. Tatiana V. Magdesieva 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(31):7074-7082
The results of extended comparative investigation of nickel(II) Schiff base complexes (containing various auxiliary chiral moieties) commonly used as a methodological platform for the asymmetric synthesis of tailor-made α-amino acids are provided. The following issues are addressed: 1) redox activity (determining the possibility for electrochemically induced reactions); 2) quantitative estimation of the reactivity of deprotonated complexes towards electrophiles; and 3) quantum-chemical estimation of noncovalent interactions in the metal coordination environment (which shed light on the origin of the stereochemical outcome observed for different stereoinductors). Possible mechanisms that determine the relationship between the stereochemical configuration of a molecule and its electronic structure are discussed. The DFT-calculated HOMO–LUMO energies and localization, as well as relative energies for the (S)- and (R)-alanine derivatives, that determine the stereoinduction efficiency in thermodynamically controlled reactions in nickel(II) coordination are provided. The computational data are supported by experimental results on the monobenzylation of glycine derivatives. 相似文献
932.
Yukimasa Aida Juntaro Nogami Dr. Haruki Sugiyama Prof. Dr. Hidehiro Uekusa Prof. Dr. Ken Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(55):12579-12588
The enantioselective synthesis of polycyclic aromatic hydrocarbon (PAH)-based planar chiral cyclophanes was achieved for the first time by the rhodium-catalyzed intramolecular regio- and enantioselective [2+2+2] cycloaddition of tethered diyne-benzofulvenes followed by stepwise oxidative transformations. The thus synthesized planar chiral bent cyclophanes, that possess bent p-terphenyl- and 9-fluorenone-cores, were converted to 9-fluorenol-based ones with excellent ee values of >99 % by diastereoselective 1,2-reduction. These 9-fluorenol-based cyclophanes exhibited high fluorescence quantum yields, which were significantly higher than that of an acyclic reference molecule (78–82 % vs. 48 %). The bending effect on the chiroptical property was also examined, which revealed that the anisotropy factors (gabs values) for electronic circular dichroism (ECD) of these 9-fluorenol-based planar chiral bent cyclophanes increase as the tether length becomes shorter. 相似文献
933.
Yang Yu Dr. Martina Delbianco 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(44):9814-9825
The conformation of a molecule strongly affects its function, as demonstrated for peptides and nucleic acids. This correlation is much less established for carbohydrates, the most abundant organic materials in nature. Recent advances in synthetic and analytical techniques have enabled the study of carbohydrates at the molecular level. Recurrent structural features were identified as responsible for particular biological activities or material properties. In this Minireview, recent achievements in the structural characterization of carbohydrates, enabled by systematic studies of chemically defined oligosaccharides, are discussed. These findings can guide the development of more potent glycomimetics. Synthetic carbohydrate materials by design can be envisioned. 相似文献
934.
Dan Xie Huan-Huan Li Yan-Hong Shi Wan-Yue Diao Ru Jiang Prof. Hai-Zhu Sun Prof. Xing-Long Wu Dr. Wenliang Li Dr. Chao-Ying Fan Prof. Jing-Ping Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(4):853-862
The Fe-based transition metal oxides are promising anode candidates for lithium storage considering their high specific capacity, low cost, and environmental compatibility. However, the poor electron/ion conductivity and significant volume stress limit their cycle and rate performances. Furthermore, the phenomena of capacity rise and sudden decay for α-Fe2O3 have appeared in most reports. Here, a uniform micro/nano α-Fe2O3 nanoaggregate conformably enclosed in an ultrathin N-doped carbon network (denoted as M/N-α-Fe2O3@NC) is designed. The M/N porous balls combine the merits of secondary nanoparticles to shorten the Li+ transportation pathways as well as alleviating volume expansion, and primary microballs to stabilize the electrode/electrolyte interface. Furthermore, the ultrathin carbon shell favors fast electron transfer and protects the electrode from electrolyte corrosion. Therefore, the M/N-α-Fe2O3@NC electrode delivers an excellent reversible capacity of 901 mA h g−1 with capacity retention up to 94.0 % after 200 cycles at 0.2 A g−1. Notably, the capacity rise does not happen during cycling. Moreover, the lithium storage mechanism is elucidated by ex situ XRD and HRTEM experiments. It is verified that the reversible phase transformation of α↔γ occurs during the first cycle, whereas only the α-Fe2O3 phase is reversibly transformed during subsequent cycles. This study offers a simple and scalable strategy for the practical application of high-performance Fe2O3 electrodes. 相似文献
935.
Dr. Pavel K. Mykhailiuk Prof. Dr. Rene M. Koenigs 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(1):89-101
Diazoacetonitrile (N2CHCN) is a small reactive diazoalkane. It has been synthesized for the first time already in 1898 by Theodor Curtius, however, did not gain much recognition in organic synthesis until recently. Only in 2015, after introduction of in situ and flow protocols for the safe generation of diazoacetonitrile, it started gaining popularity. In this minireview, the synthetic properties and applications of this valuable reagent are discussed. 相似文献
936.
Dr. Rainer Müller Dr. Mevlut Citir Dr. Sebastian Hauke Prof. Dr. Carsten Schultz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(2):384-389
Phosphatidylinositol (PI) is the biosynthetic precursor for seven phosphoinositides, important signaling lipids in cells. A membrane-permeant caged PI derivative featuring a photo-removable coumarinyl group masking the negative charge of the phosphate, as well as two enzymatically removable butyrate esters for increased lipophilicity and for preventing phosphate migration, were synthesized. Rapid cell entry and cellular labeling in fixed cells was demonstrated by a photo-cross-linkable diazirine followed by attachment of a fluorophore through click chemistry. Using this technique, we found that the multifunctional caged PI derivative resided predominantly at internal membranes but rapidly changed to the plasma membrane after uncaging. Accordingly, a preliminary proteomic analysis of the lipid–protein conjugates revealed that the two major PI transport proteins PITPα and β were prime targets of the photo-cross-linked PI derivative. 相似文献
937.
Dr. Yongqi Yao Dr. Qifu Lin Dr. Wen Yang Prof. Dr. Weitao Yang Prof. Dr. Fenglong Gu Prof. Dr. Wei Guo Prof. Dr. Dingqiao Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(25):5607-5610
A cobalt(II)-catalyzed [4+2] annulation of picolinamides with alkynes via C−H bond activation has been developed. The operationally simple annulation reaction allows for the synthesis of acyl-substituted 1H-benzoquinoline bearing multiple aromatic rings (up to 96 % yield) without co-oxidant or other oxidation factors under mild conditions. Several control experiments were carried out. This practical [4+2] annulation provides an efficient route to access highly functionalized compounds. 相似文献
938.
Nikolaos V. Tzouras Dr. Fady Nahra Dr. Laura Falivene Prof. Dr. Luigi Cavallo Marina Saab Prof. Dr. Kristof Van Hecke Dr. Alba Collado Dr. Christopher J. Collett Prof. Dr. Andrew D. Smith Prof. Dr. Catherine S. J. Cazin Prof. Dr. Steven P. Nolan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(20):4515-4519
We have been puzzled by the involvement of weak organic and inorganic bases in the synthesis of metal–N-heterocyclic carbene (NHC) complexes. Such bases are insufficiently strong to permit the presumed required deprotonation of the azolium salt (the carbene precursor) prior to metal binding. Experimental and computational studies provide support for a base-assisted concerted process that does not require free NHC formation. The synthetic protocol was found applicable to a number of transition-metal- and main-group-centered NHC compounds and could become the synthetic route of choice to form M–NHC bonds. 相似文献
939.
Dr. Abdessamad Grirrane Dr. Eleuterio Álvarez Prof. Dr. Hermenegildo García Prof. Dr. Avelino Corma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(40):8810-8818
The cationic complex [(JohnPhos–Au)3(acetylide)][SbF6] (JohnPhos=(2-biphenyl)di-tert-butylphosphine, L1) has been characterised structurally and features an acetylide–trigold(I)–JohnPhos system; the trinuclear–acetylide unit, coordinated to the monodentate bulk phosphines, adopts an unprecedented μ,η1,η2,η1 coordination mode with an additional interaction between distal phenyl rings and gold centres. Other cationic σ,π-[(gold(I)L1)2] complexes have also been isolated. The reaction of trimethylsilylacetylene with various alcohols (iPrOH, nBuOH, n-HexOH) catalysed by cationic [AuIL1][SbF6] complexes in CH2Cl2 at 50 °C led to the formation of acetaldehyde acetals with a high degree of chemo- and regioselectivity. The reaction mechanism was studied, and several organic and inorganic intermediates have been characterised. A comparative study with the analogous cationic [CuIL1][PF6] complex revealed different behaviour; the copper metal is lost from the coordination sphere leading to the formation of cationic vinylphosphonium and copper nanoparticles. Additionally, a new catalytic approach for the formation of this high-value cationic vinylphosphonium has been established. 相似文献
940.
Dr. Ruofei Cheng Prof. Dr. Zaozao Qiu Prof. Dr. Zuowei Xie 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(32):7212-7218
Iridium-catalyzed formal alkyne hydroboration with cage B−H of o-carborane has been achieved, leading to the controlled synthesis of a series of 3,6-[trans-(AlkCH=CH)]2-o-carboranes (Alk=alkyl), 3-cis-(ArCH=CH)-o-carboranes (Ar=aryl), and 3-cis-(ArCH=CH)-6-trans-(AlkCH=CH)-o-carboranes in high yields with excellent regio- and very good cis–trans selectivity. The most electron-deficient B(3,6)−H vertices favor oxidative addition on electron-rich metal centers, which is responsible for the regioselectivity. On the other hand, the configuration of the resultant olefinic units is dominated by alkyne substituents. Alkyl groups lead to a trans-configuration whereas bulky aryl substitutions result in cis-configuration. 相似文献