Nucleophile assisting leaving groups: a strategy for aliphatic 18F-fluorination.
ABSTRACT A series of arylsulfonate nucleophile assisting leaving groups (NALGs) were prepared in which the metal chelating unit is attached to the aryl ring via an ether linker. These NALGs exhibited significant rate enhancements in halogenation reactions using metal halides. Studies with a NALG containing a macrocyclic ether unit suggest that rate enhancements of these nucleophilic halogenation reactions are facilitated by stabilization of charge in the transition state rather than through strong precomplexation with metal cation. In several cases, a primary substrate containing one of the new leaving groups rivaled or surpassed the reactivity of triflates when exposed to nucleophile but was otherwise highly stable and isolable. These and previously disclosed chelating leaving groups were used in (18)F-fluorination reactions using no-carrier-added [18F]fluoride ion (t(1/2) = 109.7 min, beta+ = 97%) in CH3CN. Under microwave irradiation and without the assistance of a cryptand, such as K2.2.2, primary substrates with select NALGs led to a substantial improvement (2-3-fold) in radiofluorination yields over traditional leaving groups.
Article: Stereoretentive halogenations and azidations with titanium(IV) enabled by chelating leaving groups.Angewandte Chemie International Edition 09/2008; 47(39):7511-4. · 13.45 Impact Factor
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ABSTRACT: We report the experimental observation of traveling fronts during the electroless deposition of copper on passive steel substrates. The low-carbon steel samples are passivated in nitric acid prior to the plating experiment, thus creating a thin, protective oxide layer on the steel surface. The deposition experiments are carried out from slightly acidic (pH 3.2) copper sulfate solution and copper nitrate solution with the latter showing front propagation only in the presence of chloride ions. For up to 30 s, fronts propagate with constant velocities in the range from 0.5 to 5 mm/s depending on the experimental conditions. This phase of constant-speed propagation gives way to accelerating fronts and very rapid, spatially unstructured deposition. Front-mediated plating is observed over a wide range of cupric ion concentration and constitutes a striking and unexpected example for pattern formation in electrochemical systems.Journal of the American Chemical Society 10/2002; 124(35):10292-3. · 9.91 Impact Factor
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ABSTRACT: Tetrabutylammonium fluoride (TBAF) is prepared at low temperature by nucleophilic aromatic substitution of hexafluorobenzene with tetrabutylammonium cyanide. Adventitious water is scavenged during this synthesis by the generated hexacyanobenzene, which readily adds water under basic conditions. Contrary to expectations, TBAF is stable to Hofmann elimination in polar aprotic solvents under anhydrous conditions. Added hydroxylic solvents are shown to catalyze the decomposition of TBAF and to catalyze proton exchange with DMSO. The synthetic utility of this salt is described briefly.Journal of the American Chemical Society 03/2005; 127(7):2050-1. · 9.91 Impact Factor