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971.
Organozinc Pivalate Reagents: Segregation,Solubility, Stabilization,and Structural Insights 下载免费PDF全文
Dr. Alberto Hernán‐Gómez Emma Herd Prof. Eva Hevia Dr. Alan R. Kennedy Prof. Dr. Paul Knochel Prof. Dr. Konrad Koszinowski Sophia M. Manolikakes Prof. Robert E. Mulvey Christoph Schnegelsberg 《Angewandte Chemie (International ed. in English)》2014,53(10):2706-2710
The pivalates RZnOPiv?Mg(OPiv)X?n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D8]THF solution these reagents exist as separated Me(p‐C6H4)ZnCl and Mg(OPiv)2 species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)2 enhances the air stability of aryl zinc species by sequestering H2O contaminants. Coupling reactions of Me(p‐C6H4)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)2. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)2Li2(Cl)2(OPiv)2Zn]. 相似文献
972.
Interaction with the Surrounding Water Plays a Key Role in Determining the Aggregation Propensity of Proteins 下载免费PDF全文
Dr. Song‐Ho Chong Prof. Sihyun Ham 《Angewandte Chemie (International ed. in English)》2014,53(15):3961-3964
Understanding the molecular determinants of the relative propensities of proteins to aggregate in a cellular environment is a central issue for treating protein‐aggregation diseases and developing peptide‐based therapeutics. Despite the expectation that protein aggregation can largely be attributed to direct protein–protein interactions, a crucial role the surrounding water in determining the aggregation propensity of proteins both in vitro and in vivo was identified. The overall protein hydrophobicity, defined solely by the hydration free energy of a protein in its monomeric state sampling its equilibrium structures, was shown to be the predominant determinant of protein aggregation propensity in aqueous solution. Striking discrimination of positively and negatively charged residues by the surrounding water was also found. This effect depends on the protein net charge and plays a crucial role in regulating the solubility of the protein. These results pave the way for the design of aggregation‐resistant proteins as biotherapeutics. 相似文献
973.
Confinement of CuII–Phthalocyanine in a Bioinspired Hybrid Nanoparticle‐Assembled Structure Yields Selective and Stable Epoxidation Catalysts 下载免费PDF全文
Joydeb Manna Arlin Jose Amali Dr. Rohit Kumar Rana 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(27):8453-8457
Herein, we demonstrate that a bioinspired assembly of silica nanoparticles with polyamines as structure‐directing agents similar to that known for the biosilicification of diatoms can pave the way for the efficient encapsulation of sulfonated copper–phthalocyanine in a hybrid microcapsule structure, in which the organic component provides a capable environment for its catalytic activity in epoxidation reactions and the nanoassembled structure imparts stability. 相似文献
974.
Cover Picture: Insertion of a Single‐Molecule Magnet inside a Ferromagnetic Lattice Based on a 3D Bimetallic Oxalate Network: Towards Molecular Analogues of Permanent Magnets (Chem. Eur. J. 6/2014) 下载免费PDF全文
975.
An Unusual Triphenylphosphine Oxide Catalyzed Stereoselective 1,3‐Dichlorination of Unsaturated Ketoesters 下载免费PDF全文
Tian‐Yang Yu Yao Wang Peng‐Fei Xu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):98-101
An unusual Ph3PO‐catalyzed stereoselective 1,3‐dicholorination of an unsaturated ketoester has been developed. The novel activation mode involved in this cascade reaction can promote consecutively elusive transformations. The products were obtained with good yields and excellent stereoselectivities. This reaction makes important complementation to the limitations associated with the field of dichlorination. 相似文献
976.
Manganese‐Corrole Complexes as Versatile Catalysts for the Ring‐Opening Homo‐ and Co‐Polymerization of Epoxide 下载免费PDF全文
Dr. Carine Robert Takahiro Ohkawara Prof. Dr. Kyoko Nozaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(16):4789-4795
Manganese‐corrole complexes in combination with a co‐catalyst [PPN]X ([PPN]+=bis(triphenylphosphoranylidene)iminium) were found to be new versatile catalysts for the polymerization of epoxides, copolymerization of epoxides with CO2, and copolymerization of epoxides with cyclic anhydrides affording a wide range of polymeric materials. This work should allow the synthesis of new types of improved innovative (co)polymers with original properties and would clearly increase the number of applications for polyesters, polycarbonates, and polyethers. 相似文献
977.
Dr. Tao Xu Dr. Chi Wai Cheung Prof. Dr. Xile Hu 《Angewandte Chemie (International ed. in English)》2014,53(19):4910-4914
Iron catalysis has been developed for the intermolecular 1,2‐addition of perfluoroalkyl iodides to alkynes and alkenes. The catalysis has a wide substrate scope and high functional‐group tolerance. A variety of perfluoroalkyl iodides including CF3I can be employed. The resulting perfluoroalkylated alkyl and alkenyl iodides can be further functionalized by cross‐coupling reactions. This methodology provides a straightforward and streamlined access to perfluoroalkylated organic molecules. 相似文献
978.
Dr. Qing‐Yuan Yang Prof. Dr. Jean‐Marie Lehn 《Angewandte Chemie (International ed. in English)》2014,53(18):4572-4577
White‐light‐emitting materials and devices have attracted enormous interest because of their great potential for various lighting applications. We herein describe the light‐emitting properties of a series of new difunctional organic molecules of remarkably simple structure consisting of two terminal 4‐pyridone push–pull subunits separated by a polymethylene chain. They were found to emit almost “pure” white light as a single organic compound in the solid state, as well as when incorporated in a polymer film. To the best of our knowledge, they are the simplest white‐light‐emitting organic molecules reported to date. 相似文献
979.
Daniel B. Moore Prof. Matt Beekman Dr. Sabrina Disch Dr. David C. Johnson 《Angewandte Chemie (International ed. in English)》2014,53(22):5672-5675
Telluride misfit layer compounds are reported for the first time. These compounds were synthesized using a novel approach of structurally designing a precursor that would form the desired product upon low‐temperature annealing, which allows the synthesis of kinetically stable products that do not appear on the equilibrium phase diagram. Four new compounds of the [(PbTe)1.17]m(TiTe2)n family are reported, and their structures were examined by a variety of X‐ray diffraction techniques. 相似文献
980.
M. Sc. Moritz C. Baier Dr. Martin A. Zuideveld Prof. Dr. Stefan Mecking 《Angewandte Chemie (International ed. in English)》2014,53(37):9722-9744
Research on “post‐metallocene” polymerization catalysis ranges methodologically from fundamental mechanistic studies of polymerization reactions over catalyst design to material properties of the polyolefins prepared. A common goal of these studies is the creation of practically useful new polyolefin materials or polymerization processes. This Review gives a comprehensive overview of post‐metallocene polymerization catalysts that have been put into practice. The decisive properties for this success of a given catalyst structure are delineated. 相似文献