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41.
The synthesis of a novel spiro[1-benzofuran-2,4'-piperidin]-3-one scaffold has been achieved in five steps with an overall yield of 47%. The versatility of the spiropiperidine scaffold in the context of library synthesis is exemplified by selective and sequential derivatisation of the amino and aryl bromide functional groups, including the development of multi-step telescope reaction matrices. 相似文献
42.
Rowan SJ Cantrill SJ Cousins GR Sanders JK Stoddart JF 《Angewandte Chemie (International ed. in English)》2002,41(6):898-952
Dynamic covalent chemistry relates to chemical reactions carried out reversibly under conditions of equilibrium control. The reversible nature of the reactions introduces the prospects of "error checking" and "proof-reading" into synthetic processes where dynamic covalent chemistry operates. Since the formation of products occurs under thermodynamic control, product distributions depend only on the relative stabilities of the final products. In kinetically controlled reactions, however, it is the free energy differences between the transition states leading to the products that determines their relative proportions. Supramolecular chemistry has had a huge impact on synthesis at two levels: one is noncovalent synthesis, or strict self-assembly, and the other is supramolecular assistance to molecular synthesis, also referred to as self-assembly followed by covalent modification. Noncovalent synthesis has given us access to finite supermolecules and infinite supramolecular arrays. Supramolecular assistance to covalent synthesis has been exploited in the construction of more-complex systems, such as interlocked molecular compounds (for example, catenanes and rotaxanes) as well as container molecules (molecular capsules). The appealing prospect of also synthesizing these types of compounds with complex molecular architectures using reversible covalent bond forming chemistry has led to the development of dynamic covalent chemistry. Historically, dynamic covalent chemistry has played a central role in the development of conformational analysis by opening up the possibility to be able to equilibrate configurational isomers, sometimes with base (for example, esters) and sometimes with acid (for example, acetals). These stereochemical "balancing acts" revealed another major advantage that dynamic covalent chemistry offers the chemist, which is not so easily accessible in the kinetically controlled regime: the ability to re-adjust the product distribution of a reaction, even once the initial products have been formed, by changing the reaction's environment (for example, concentration, temperature, presence or absence of a template). This highly transparent, yet tremendously subtle, characteristic of dynamic covalent chemistry has led to key discoveries in polymer chemistry. In this review, some recent examples where dynamic covalent chemistry has been demonstrated are shown to emphasise the basic concepts of this area of science. 相似文献
43.
Chang T Heiss AM Cantrill SJ Fyfe MC Pease AR Rowan SJ Stoddart JF White AJ Williams DJ 《Organic letters》2000,2(19):2947-2950
Dipyrido[24]crown-8 (DP24C8) has been synthesized and shown to form [2]pseudorotaxanes spontaneously with dibenzylammonium ions. These complexes, which have been demonstrated by (1)H NMR spectroscopy to form faster in solution than when the macrocyclic polyether is dibenzo[24]crown-8 (DB24C8), are also stronger than their DB24C8 counterparts. One of the [2]pseudorotaxanes has been used to construct a [2]rotaxane (see above) comprising a dumbbell-shaped component based on a dibenzylammonium ion which is encircled by a DP24C8 macrocycle and terminated by (triphenylphosphonium)methyl stoppers. 相似文献
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Farrera JA Hidalgo-Fernández P Hannink JM Huskens J Rowan AE Sommerdijk NA Nolte RJ 《Organic & biomolecular chemistry》2005,3(13):2393-2395
Monovalent ligand and divalent ligand have been synthesized, and their thermodynamic parameters of complexation to avidin and streptavidin have been analyzed in terms of multivalent binding. 相似文献
46.
K. R. Rowan E. M. Holt 《Acta Crystallographica. Section C, Structural Chemistry》1996,52(9):2207-2212
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Anderson J.G. Rowan N.J. MacGregor S.J. Fouracre R.A. Farish O. 《IEEE transactions on plasma science. IEEE Nuclear and Plasma Sciences Society》2000,28(1):83-88
The lethality of high-intensity pulsed-light emissions from low and high ultraviolet (UV) light sources on predetermined microbial populations has been investigated. Prior to treatment, the bacterial enteropathogens Bacillus cereus, Escherichia coli, and Salmonella enteritidis and the food-spoilage fungi Aspergillus niger and Fusarium culmorum were seeded separately onto the surface of either tryptone soya yeast extract or malt extract agar plates. Prescribed microbial population densities were applied to the test media and these samples were exposed to one of two light sources. These were low-pressure, xenon filled, flash lamps that produced either high or low UV intensities. They were operated in pulsed mode, being driven by a stacked Blurnlein table generator. Microbial samples were treated by exposure to different numbers of light pulses. The treated bacterial populations were reduced by ~8 log orders after 1000 light-pulses of the higher UV intensity light and the fungal counts had a corresponding reduction of 4.5 log orders. The fungus, Aspergillus niger, was shown to be significantly more resistant in spore form to the intense UV light compared with Fusarium culmorum. This resistance has been attributed to the high level of UV absorbance associated with the dark pigment present in A. niger. The pulsed light source of lower UV intensity was shown to be significantly less effective in reducing microbial populations 相似文献