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This work demonstrates that a global ring current can be promoted in a macrocycle by adjusting its oxidation state to suppress the local ring currents of its components.The discovery of ring currents around a molecule with a circumference of 7 nanometres, at room temperature, shows that quantum coherence can persist in surprisingly large molecular frameworks.Evolution of functional cyclohexadiene-based synthetic reagents: the importance Suites of new precursors designed around a cyclohexadiene core and intended to mediate "clean" radical chain syntheses have been prepared and tested. 1-Functionalized cyclohexa-2,5-dienes were found to readily donate H-atoms, and the resulting cyclohexadienyl radicals rapidly extruded their functional group as a free radical, because this beta-scission restored aromaticity to the ring. This concept was employed to generate designer radicals from esters of the corresponding alcohols with 1-methyl- or 1-phenylcyclohexa-2,5-diene-1-carboxylic acids. In a similar way, pre-adapted carbamoyl radicals were obtained from cyclohexadienyl-amides and proved advantageous for syntheses of alpha- and beta-lactams.<br /><br /> [http://allinno.com/news/166.html Seebio Photolyzable Acid Precursor] substituted carbamoyl radicals cyclized successfully in convenient syntheses of dihydroindolin-2-ones with N-functionality at the 3-position. Similarly, silicon-centered radicals were obtained from 1-silylated cyclohexadienes, and these reagents proved to be very efficient, environmentally benign organotin hydride substitutes. Radical reactions including reductions, cyclizations, intermolecular additions, and hydrosilylations were carried out in high yields with this reagent. Other heteroatom-centered radicals, especially N-centered radicals, were obtained from appropriate cyclohexadienes enabling chain hydroaminations to be conducted. Several of the cyclohexadiene precursors proved to be useful for electron paramagnetic resonance (EPR) spectroscopic purposes, and this enabled rate constants for fragmentations of the cyclohexadienyl radicals to be obtained. Kinetic data for H-atom abstraction from cyclohexadienes, the second propagation step of the chain processes, was derived from customized radical clocks and from EPR measurements. In this way, conceptual tools were developed for improving future synthetic methodology based Spirocyclic hypervalent iodine(III)-mediated radiofluorination of non-activated Medical Imaging Sciences, Massachusetts General Hospital &amp; Department of Radiology, Harvard Medical School, 55 Fruit Street, Boston, MA 02114, USA [2].<br /><br />Medical Imaging Sciences, Massachusetts General Hospital &amp; Department of Radiology, Harvard Medical School, 55 Fruit Street, Boston, MA 02114, USA.Fluorine-18 (t½=109 min) is the most commonly used isotope to prepare radiopharmaceuticals for molecular imaging by positron emission tomography (PET). Nucleophilic aromatic substitution reactions of suitably activated (electron-deficient) aromatic substrates with no-carrier-added [(18)F]fluoride ion are routinely carried out in the synthesis of radiotracers in high specific activities. Despite extensive efforts to develop a general (18)F-labelling technique for non-activated arenes there is an urgent and unmet need to achieve this goal. Here we describe an effective solution that relies on the chemistry of spirocyclic hypervalent iodine(III) complexes, which serve as precursors for rapid, one-step regioselective radiofluorination with [(18)F]fluoride. This methodology proves to be efficient for radiolabelling a diverse range of non-activated functionalized arenes and heteroarenes, including arene substrates bearing electron-donating groups, bulky ortho functionalities, benzylic substituents and meta-substituted electron-withdrawing groups. Polyfunctional molecules and a range of previously elusive (18)F-labelled building blocks, compounds and radiopharmaceuticals are synthesized.<br /><br />Cation-pi interactions: an energy decomposition analysis and its implication in Supercomputer Institute, University of Minnesota, Minneapolis, Minnesota 55455, The nature and strength of the cation-pi interaction in protein-ligand binding are modeled by considering a series of nonbonded complexes involving N-substituted piperidines and substituted monocylic aromatics that mimic the delta-opioid receptor-ligand binding. High-level ab initio quantum mechanical calculations confirm the importance of such cation-pi interactions, whose intermolecular interaction energy ranges from -6 to -12 kcal/mol. A better understanding of the electrostatics, polarization, and other intermolecular interactions is obtained by appropriately decomposing the total interaction energy into their individual components. The energy decomposition analysis is also useful for parametrizing existing molecular mechanics force fields that could then account for energetic contributions arising out of cation-pi interactions in biomolecules.