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191.
The title cyclohexenone 1d undergoes photodimerization selectively at the exocyclic C?C bond to give a 1 : 1 mixture of 1,2‐dialkynyl‐1,2‐dimethylcyclobutanes 6 and 7 . On irradiation in the presence of 2,3‐dimethylbuta‐1,3‐diene, 1d affords bicyclo[8.4.0]tetradeca‐1,2,3,7‐tetraen‐11‐one 9 . This – formal – (6+4)‐cycloadduct undergoes quantitative isomerization to 3‐cycloheptadienyl‐2,5,5‐trimethylcyclohex‐2‐enone 11 on treatment with basic silica gel. 相似文献
192.
Grzegorz Mlostoń Marta Woźnicka Józef Drabowicz Anthony Linden Heinz Heimgartner 《Helvetica chimica acta》2008,91(8):1419-1429
The reactions of 3‐phenyl‐1‐azabicyclo[1.1.0]butane with α‐chlorosulfenyl chlorides and sulfinyl chlorides lead to the corresponding sulfenamides and sulfinamides, respectively, which possess an azetidine ring. It is proposed that a two‐step mechanism occurs involving an intermediate carbenium ion, which is formed by the addition of the electrophile at the N‐atom and cleavage of the N(1)? C(3) bond. The structures of 9b and 10b are established by X‐ray crystallography. 相似文献
193.
Guang‐Yu Yang Wei‐Lie Xiao Ying Chang Rui‐Rui Wang Jian‐Xin Pu Xue‐Mei Gao Chun Lei Yang Lu Yong‐Tang Zheng Han‐Dong Sun 《Helvetica chimica acta》2008,91(10):1871-1878
Three new highly oxygenated nortriterpenoids, wilsonianadilactones A–C ( 1 – 3 ), together with twelve known ones, i.e., 4 – 15 , were isolated from the leaves and stems of Schisandra wilsoniana. Their structures were established by means of extensive analysis of spectroscopic data, and compound 1 was further confirmed by X‐ray crystallographic diffraction. Compounds 1 – 3 showed weak anti‐HIV‐1 activity with EC50 values of 23.5, 55.5, and 66.4 μg/ml, respectively. 相似文献
194.
A Computational and Experimental Approach Linking Disorder,High‐Pressure Behavior,and Mechanical Properties in UiO Frameworks
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Claire L. Hobday Ross J. Marshall Colin F. Murphie Jorge Sotelo Tom Richards Dr. David R. Allan Prof. Tina Düren Dr. François‐Xavier Coudert Dr. Ross S. Forgan Dr. Carole A. Morrison Dr. Stephen A. Moggach Dr. Thomas D. Bennett 《Angewandte Chemie (International ed. in English)》2016,55(7):2401-2405
Whilst many metal–organic frameworks possess the chemical stability needed to be used as functional materials, they often lack the physical strength required for industrial applications. Herein, we have investigated the mechanical properties of two UiO‐topology Zr‐MOFs, the planar UiO‐67 ([Zr6O4(OH)4(bpdc)6], bpdc: 4,4′‐biphenyl dicarboxylate) and UiO‐abdc ([Zr6O4(OH)4(abdc)6], abdc: 4,4′‐azobenzene dicarboxylate) by single‐crystal nanoindentation, high‐pressure X‐ray diffraction, density functional theory calculations, and first‐principles molecular dynamics. On increasing pressure, both UiO‐67 and UiO‐abdc were found to be incompressible when filled with methanol molecules within a diamond anvil cell. Stabilization in both cases is attributed to dynamical linker disorder. The diazo‐linker of UiO‐abdc possesses local site disorder, which, in conjunction with its longer nature, also decreases the capacity of the framework to compress and stabilizes it against direct compression, compared to UiO‐67, characterized by a large elastic modulus. The use of non‐linear linkers in the synthesis of UiO‐MOFs therefore creates MOFs that have more rigid mechanical properties over a larger pressure range. 相似文献
195.
Radiation Damage and Racemic Protein Crystallography Reveal the Unique Structure of the GASA/Snakin Protein Superfamily
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Ho Yeung Dr. Christopher J. Squire Yuliana Yosaatmadja Dr. Santosh Panjikar Gemma López Prof. Dr. Antonio Molina Prof. Dr. Edward N. Baker Dr. Paul W. R. Harris Prof. Dr. Margaret A. Brimble 《Angewandte Chemie (International ed. in English)》2016,55(28):7930-7933
Proteins from the GASA/snakin superfamily are common in plant proteomes and have diverse functions, including hormonal crosstalk, development, and defense. One 63‐residue member of this family, snakin‐1, an antimicrobial protein from potatoes, has previously been chemically synthesized in a fully active form. Herein the 1.5 Å structure of snakin‐1, determined by a novel combination of racemic protein crystallization and radiation‐damage‐induced phasing (RIP), is reported. Racemic crystals of snakin‐1 and quasi‐racemic crystals incorporating an unnatural 4‐iodophenylalanine residue were prepared from chemically synthesized d ‐ and l ‐proteins. Breakage of the C?I bonds in the quasi‐racemic crystals facilitated structure determination by RIP. The crystal structure reveals a unique protein fold with six disulfide crosslinks, presenting a distinct electrostatic surface that may target the protein to microbial cell surfaces. 相似文献
196.
Using a one-pot synthetic approach, a single isomer of bis(diethylenetriamine)cobalt(III) cation, [Co(dien)2]3+ is obtained in bulk from the isomeric mixture (s-fac : u-fac : mer is 7 : 28 : 65) using sodium salts of benzoates (BBz-bromobenzoate, DNBz-dinitrobenzoate, MBz-methylbenzoate) in aqueous medium. Herein, we report the syntheses and characterization of three complexes of composition mer-[Co(dien)2]Cl(p-BBz)2·H2O (1), s-fac-[Co(dien)2](o,p-DNBz)3·H2O (2) and mer-[Co(dien)2]Cl(p-MBz)2·4H2O (3) in the continuation of our earlier work, where benzoate (Bz), p-chlorobenzoate (CBz), p-nitrobenzoate (NBz) and p-aminobenzoate (ABz) were used. The isomeric identification of complex cation was initially made on the basis of spectroscopic characterization (UV–visible, IR and NMR). The binding properties of [Co(dien)2]3+ with benzoates (p-BBz, o,p-DNBz, p-MBz, Bz, CBz, NBz or ABz) have been studied using standard UV–visible spectroscopic titrations in aqueous medium and comparison indicate ion association constants of s-fac > mer. The single-crystal X-ray diffraction structure analysis of 3 reveals the presence of discrete ions ([Co(dien)2]3+, chloride, p-MBz) along with four lattice water molecules. The structure of 3, with formula [Co(dien)2](p-MBz)2Cl·4H2O, consists of alternating layers made of benzoate ions and layers made of [Co(dien)2]3+, chloride and water molecules. These layers result in the formation of their respective columns and intermolecular cohesion of p-MBz within the columns of [Co(dien)2]3+ is achieved via electrostatic and H-bonding interactions. 相似文献
197.
198.
Dr. Ricardo Rodriguez Dr. Yohan Contie Raphael Nougué Dr. Antoine Baceiredo Dr. Nathalie Saffon‐Merceron Dr. Jean‐Marc Sotiropoulos Dr. Tsuyoshi Kato 《Angewandte Chemie (International ed. in English)》2016,55(46):14355-14358
Phosphine‐stabilized silylenes react with silanes and a phosphine by silylene insertion into E?H σ‐bonds (E=Si,P) at room temperature to give the corresponding silanes. Of special interest, the process occurs reversibly at room temperature. These results demonstrate that both the oxidative addition (typical reaction for transient silylenes) and the reductive elimination processes can proceed at the silicon center under mild reaction conditions. DFT calculations provide insight into the importance of the coordination of the silicon center to achieve the reductive elimination step. 相似文献
199.
Giant Hysteretic Sorption of CO2: In Situ Crystallographic Visualization of Guest Binding within a Breathing Framework at 298 K
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Dr. Prem Lama Dr. Himanshu Aggarwal Charl X. Bezuidenhout Prof. Leonard J. Barbour 《Angewandte Chemie (International ed. in English)》2016,55(42):13271-13275
A dynamic ZnII‐MOF has been shown to exhibit extreme breathing behavior under gas pressure. The very narrow pore form of the activated framework opens up in the presence of carbon dioxide, thus making it a suitable material for CO2 capture. Sorption of CO2 at 298 K and relatively high pressure clearly shows a two‐step isotherm with giant hysteresis for the second step. In‐situ single‐crystal diffraction analysis was carried out under CO2 gas pressure at 298 K using an environmental gas cell in order to visualize the interaction between CO2 and the host framework. The results are well supported by pressure‐gradient differential scanning calorimetry (P‐DSC) and variable‐pressure powder X‐ray analysis. Theoretical calculations have been carried out in order to further back up the crystallographic data. 相似文献
200.
Dr. Russell W. Driver Prof. Timothy D. W. Claridge Prof. Steve Scheiner Prof. Martin D. Smith 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16513-16521
The precise role of non‐conventional hydrogen bonds such as the C?H???O interaction in influencing the conformation of small molecules remains unresolved. Here we survey a series of β‐turn mimetics using X‐ray crystallography and NMR spectroscopy in conjunction with quantum calculation, and conclude that favourable torsional and electronic effects are important for the population of states with conformationally influential C?H???O interactions. Our results also highlight the challenge in attempting to deconvolute a myriad of interdependent noncovalent interactions in order to focus on the contribution of a single one. Within a small molecule that is designed to resemble the complexity of the environment within peptides and proteins, the interplay of different steric burdens, hydrogen‐acceptor/‐donor properties and rotational profiles illustrate why unambiguous conclusions based solely on NMR chemical shift data are extremely challenging to rationalize. 相似文献