Approaches to the synthesis of arisugacin A

Approaches to the synthesis of the important acetylcholinesterase inhibitor, arisugacin A, are described. Two different routes to the key AB ring system are described: the first utilizes an intramolecular Diels-Alder reaction on a furan substrate and the second a 6π-electrocyclization of a substituted triene followed by cycloaddition with singlet oxygen. The successful synthesis of a fully functionalized AB ring system of arisugacin A, the tetraol 52 from hydroxy-β-ionone 22 in 16 steps and 9.3% overall yield is described. Several useful synthetic transformations to this molecule and its analogues are reported, e.g., the formation of the furan Diels-Alder cycloadduct 14 and its conversion into the oxa-bridged structures 17 and 21, the preparation of the dienes 25 and 26 and the conversion of the later into the endoperoxide 30 and its diol 36, the preparation of the endoperoxide 40 and the oxa-bridged system 42, and finally the use of the enelactone 43 and its ultimately successful conversion into 52. In addition, several novel rearrangements are described, producing the unusual compounds 62, 65, and 67. Finally, the successful coupling of the pyrone unit to the AB ring system is described to give compounds 70 and 71. The novel reduction of these compounds to the cyclic ether 74 is described.     

Approaches to the total synthesis of phomactins

The macrocyclic triene 34, an advanced intermediate for synthesis of phomactins, has been synthesized using the 2,3-Wittig rearrangement of the propargylic ether 21 as a key step.     

Towards understanding of protein adsorption behavior on plasma polymerized pyrrole film

Plasma polymerized pyrrole-like (PPpy) films exhibit good environmental stability and offer high reactivity with biomolecules. The present paper follows on from previous work on PPpy films applied as DNA immobilization/hybridization and describes the adsorption kinetics of bovine serum albumin (BSA) on PPpy films. Atom force microscopy was used to detect the surface roughness of PPpy surfaces obtained at different input powers or for different polymerization time, including the surface roughness before and after BSA adsorption. The influence of experimental conditions (i.e., the plasma input power, the polymerization time, the concentration of BSA, and the pH values of buffer solutions) on protein adsorption was investigated in situ by Surface plasmon resonance spectroscopy (SPR). SPR analysis confirmed the differently dynamic adsorption behavior of BSA on PPpy films under various experimental conditions. The adsorption constant, K _a , was deduced from Langmuir isotherm equations, which were simulated using experimental data collected by SPR and electrochemical impedance spectroscopy (EIS). Analysis of the combination data of SPR and EIS indicates that PPpy films under various conditions show completely different adsorption behaviors and could be applied as biomaterials for electrochemical protein sensing or as protein-resistant.      

Synthetic Approaches to Selenoesters

Selenoesters are compounds of great synthetic relevance since they can be used in several types of chemical transformations and mainly due to their great capacity in the formation of acyl radicals. Therefore, the scientific community has been developing several methods for the synthesis of this class of molecules. This review will address the synthesis of these compounds from different starting materials, such as carboxylic acids derivatives (acid chlorides and anhydrides), aldehydes, selenoacetylenes and miscellaneous methods.     

Approaches to the regiospecific synthesis of Anthracycline antibiotics

Synthetic approaches to anthracycline antibiotics were studied through the use of Claisen rearrangements on 1-methallyloxy-5-methoxyantraquinone (9) which required reducing conditions to proceed through a hydroquinone intermediate in situ. 1-(2′-Methylene-4′-pentenoxy)-5-methoxyanthraquinone (13) underwent a similar reductive rearrangement but also produced a spiro compound 16 as a result of an ene reaction between the phenol and side chain double bond. 1-Hydroxy-2-methally-5-methoxyanthraquinone (11) could not be oxidized to quinizarin 17. 1-Hydroxy-2-methally-5,9,10-trimethoxyanthracene (21) was oxidatively coupled to the dimer at C-2. Dimer 23 reacted with diazomethane to form a 1,3-dipolar adduct 24.     

New Approaches to the Synthesis of Metal Carbenes

Metal carbenes usually possess versatile reactivities that are controlled by the presence of both the metals and the ligands. Diazo compounds are commonly used for the generation of such species through elimination of nitrogen. However, they are often unstable, explosive, and toxic, which limits their applications in large‐scale syntheses. Thus, identifying sustainable and safe surrogates for the generation of metal carbenes has attracted great attention. In this Review, we summarize some of the most important breakthroughs in the generation, catalytic reactions, and selectivity control of metal carbenes from non‐diazo starting compounds.     

Approaches to the synthesis of 3-fluoroshikimic acids

Exploitation of the dual dehydrating and fluorodeoxygenating properties of the dialkylaminosulfurtrifluorides has allowed access to the C3-fluorinated analogues of (−)-shikimic acid.     

Approaches to the preparation of carborane-containing carbosilane compounds

[Structure: see text] A novel type of carborane cluster assembly has been successfully prepared using carbosilane derivatives as a scaffold. Two synthetic routes have been used: One involves the reaction of a carbosilane containing terminal Si-Cl functions with the lithium salt of the phenyl-o-carborane, and the second one consists of a highly efficient hydrosilylation of tetravinylsilane with the corresponding carboranylsilane. The crystal structure of this carborane-containing carbosilane compound has been determined by X-ray diffraction.     

Approaches to the synthesis of optically pure helicates

Methods by which helical bimetallic assemblies may be accessed as single isomers are described and reviewed. While there are a number of notable successes, the conclusion is made that no existing approach satisfies the criteria which will allow these fascinating compounds to emerge from the synthetic research laboratory environment to practical application in e.g. healthcare. For this to be achieved the compounds must be optically pure and non-racemising, soluble and chemically stable in water, readily available on a large scale, chemically diverse and synthetically robust.     

Approaches to the Solid-Phase Extraction of Equine Urine

Three approaches to the solid-phase extraction of horse urine are reviewed. Simple reversed-phase SPE may be coupled with a chromatographic technique that provides a second stage of separation in the presence of a high matrix background. Pre-extraction of the urine or hydrolysed urine allows the elimination of salts and other matrix related interferences prior to the primary extraction. Serial processing of urine, hydrolysed urine or pre-extracted samples through specialty sorbents allow speciation of a single sample into many different classes suitable for Systematic Toxicological Analysis analysis by GC-MS or LC-MS. The multi-eluate approach allows significant reduction of the matrix background when compared with parallel SPE of a sample.     

赤霉素合成的研究进展

本文综述了近年来赤霉素全合成和半合成研究的进展,对有关新合成方法也作了介绍。     

Contribution to understanding of the molecular dynamics in liquids

The dielectric relaxation spectroscopy is used for studying the orientational molecular dynamics in the isotropic (I) and nematic (N) phases of two mesogenic liquids composed of the molecules of similar structure and length, but of an essentially different polarity: n-heptylcyanobiphenyl, C(7)H(15)PhPhCN, 7CB (molecular dipole moment mu approximately 5D) and 4-(trans-4'-n-hexylcyclohexyl)isothiocyanatobenzene, C(6)H(13)CyHxPhNCS, 6CHBT (mu approximately 2.5D); advantageously, the temperatures of the I-N phase transition for the two compounds are very close to each other (T(NI) = 316.6 +/- 0.2 K). It is shown that regardless of the differences in polarity of 7CB and 6CHBT molecules and their abilities in dipolar aggregation, the values and temperature dependences of the relaxation time (corresponding to the rotational diffusion of the molecules around their short axis) are very close to each other, in both the isotropic and nematic phases of the liquids studied. Therefore, the data show that the dielectric relaxation processes occurring in dipolar liquids in the isotropic and nematic states lead through the rotational diffusion of individual molecules and the diffusion seems to be not influenced by the intermolecular interactions.     

Approaches to phenazine-derived N-isosteres of anthracyclinones

1-Hydroxyphenazine 5,10-dioxide showed antitumor properties against mouse leukemia P388. It also participated in biochemical mechanisms of quinoid antitumor agents, as indicated by inhibition of radiolabeled DNA-RNA precursors in cultured leukemia L1210 cells and by stimulation of oxygen consumption in mammalian microsomes. This suggests that the isosteric di-N-oxide system may be a biologically active substitute for 1,4-quinone, and that di-N-oxides of tetrahydrobenzo[b]phenazines can be explored as anthracyclinone N-isosteres. As potential synthetic intermediates, 7,8,9,10-tetrahydro-6,11-dihydroxybenzo[b]-phenazines have been prepared by 1) Diels-Alder addition of phenazine-1,4-quinone and 1-methoxy-3-(trimethylsilyloxy)-1,3-butadiene to give isolable but labile adducts and 2) condensation of 6,7-diamino-1,2,3,4-tetrahydro-2-hydroxy-5,8-dimethoxy-2-naphthoic acid with 3-methoxy-1,2-quinone. Attempts at N-oxidation gave instead oxidation of the 6,11-hydroquinone ring to quinone, regardless of hydroxyl protection. Despite previous literature indications, we have been unable to synthesize the 1,4-dihydroxyphenazine 5,10-dioxide system. We conclude that this hydroxyl substitution pattern (1,4) in an adjacent ring must be avoided in the redesign of anthracyclinone isosteres that have di N-oxide in place of quinone.     

Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution

This work aims to investigate more sustainable reaction conditions for the synthesis of metallophthalocyanines. Anisole, glycerol and their mixtures have been investigated as reaction media for the tetramerization of phthalonitriles. Acetates of three divalent first-transition metal cations, Co(II), Cu(II) and Zn(II), were used and several bases were tested, depending on the chosen substrates and reaction conditions, with a view to making the whole process more sustainable while ensuring its scalability. Unsubstituted phthalocyanines were synthesized to analyze the behavior of the different metal ions in terms of reactivity in the new reaction media, resulting in a general Cu > Co > Zn trend, while the nonpolar tetra-tert-butyl substitution was investigated to evaluate the synthesis of soluble derivatives in the new conditions. Furthermore, the potassium hydroxide (KOH)-aided statistical synthesis of the unsymmetrical 9(10), 16(17), 23(24)-tri-tert-butyl-2-iodophthalocyaninato zinc(II), starting from 4-tert-butylphthalonitrile and 4-iodophthalonitrile in a glycerol/anisole mixture, proceeded with a satisfactory 26% yield. Our results provide insights into the investigation of new reaction environments and the understanding of their strengths and weaknesses, with a view to further increasing the sustainability of the synthesis of metallomacrocycles with high added value while lowering their production cost.     

On the way of understanding the behavior of nanometer-scale metallic particles toward the adsorption of CO and NO molecules

Previously, we have proposed a relationship between the adsorption modes of a simple molecule (NO) and the behavior of the nanometer-scale monometallic clusters after this adsorption. More precisely, a set of experiments seems to show that dissociative adsorption of NO leads to the sintering of nanometer-scale metallic particles (NSMPs), whereas molecular adsorption is related to the oxidation. Although numerous investigations have been published on catalytic or electrocatalytic reactions where the interaction between carbon monoxide and NSMPs is involved, only a few studies have been dedicated to the adsorption of CO on NSMPs. This purely energetic approach is discussed through different results already published in the literature and through some recent theoretical calculations related to solid state physics. Although interesting and systematic results are gathered here and are partly explained, this adsorption process still remains a challenge.     

Approaches to polymeric mechanochromic materials

Mechanochromic materials respond to mechanical stimuli with a change of their optical properties. Such materials are of interest for many technological applications and support fundamental research as they help improving the understanding of stress transfer in polymeric objects and aid in the identification of the processes that lead to mechanical failure. In this highlight, different approaches are discussed that permit the design of polymeric materials, which signal mechanical stresses through a chromic response. This highlight emphasizes materials that exhibit mechanically induced changes of their intrinsic absorption or emission properties. These responses almost exclusively originate from changes of molecular structure, conformational rearrangements, or disruption of intermolecular interactions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 640–652