A series of ten electron deficient aza–BODIPYs were prepared through a facile nitration strategy where either one, two, or four nitro groups can be regioselectively attached which represents a novel...
A series of boron, aluminum, gallium, and indium chelates containing the underexplored bis(phenolate) aza-dipyrromethene (aza-DIPY) core were prepared. These compounds were found to possess near-infrared absorption and emission profiles in the 710 to 770 nm domain and exhibit quantum yield values up to 14%. X-ray diffraction analysis revealed that heavier group 13 bis(phenolate) aza-DIPY chelates possessed octahedral geometries with either THF or pyridine groups occupying the axial positions as opposed to the tetrahedral geometry of the boron chelate.
Roussi's landmark work on the generation of 1,3dipoles from tertiary amine N-oxides has not reached its full potential since its underlying mechanism is neither well explored nor understood. Two competing mechanisms were previously proposed to explain the transformation involving either an iminium ion or a diradical intermediate. Our investigation has revealed an alternative mechanistic pathway that explains experimental results and provides significant insights to guide the creation of new Noxide reagents beyond tertiary alkylamines for direct synthetic transformations. Truhlar's M06-2x functional and Møller−Plesset second-order perturbation theory with Dunning's [jul,aug]-cc-pv[D,T]z basis sets and discrete-continuum solvation models were employed to determine activation enthalpies and structures. During these mechanistic explorations, we discovered a unique multiion bridged pathway resulting from the rate-determining step, which was energetically more favorable than other alternate mechanisms. This newly proposed mechanism contains no electrophilic intermediates, strengthening the reaction potential by broadening the reagent scope and limiting the possible side reactions. This thoroughly defined general mechanism supports a more direct route for improving the use of N-oxides in generating azomethine ylide−dilithium oxide complexes with expanded functional group tolerance and breadth of chemistry.
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