Accelerated CarbonCarbon Bond‐Forming Reactions in Preparative Electrospray

Abstract

The chemistry of life occurs in spatially limited volumescells-the structural and functional units of living organisms. Biochemical reactions can also take place within the confines of interfaces, for example, those between air and water [1] in atmospheric aerosols. These unique chemical environments can be mimicked by performing reactions in enclosed volumes, for example, in micelles or microemulsions. [1f, 2] Inside these compartmentalized liquids, limiting phase boundaries as well as significant changes in local concentrations can enhance reaction rates, [2a] induce regioselectivity, [3] and help to overcome reagent incompatibilities. [2b] Although electrospray has been used for the production of inorganic nanoparticles [4] and thin organic polymer films, [5] it is most widely associated with ionization in mass spectrometry (MS). [6] Recent MS experiments have revealed that charged microdroplets can serve as the locus for simple as well as complex and multistep reactions. [7] Here we show that ordinary carbon-carbon bond reactions can be performed on a microscale by collecting the sprayed droplets. As a model system we investigated the basecatalyzed Claisen-Schmidt condensation of 1-indanone (1) and 4-chlorobenzaldehyde (2) (see Scheme 1). Absorption

Bottom‐Up C60 Fullerene Construction from a Fluorinated C60H21F9 Precursor by Laser‐Induced Tandem Cyclization

“…In general, our finding opens new possibilities for the synthesis of carbon-based nanomaterials. Since synthesis under MS conditions can generally be extended to the micro-preparative scale, [21] the approach can give access to highly interesting systems, which cannot be obtained by alternative methods. In particular, the approach seems to be attractive for the isomer specific synthesis of highly reactive non-IPR fullerenes.…”

Reactive Charged Droplets for Reduction of Matrix Effects in Electrospray Ionization Mass Spectrometry

“…Our motivation was to use the accelerated reaction rates typical under the charged micro-droplet environment [11][12][13][14][15] for on-line analytes modification, and thus enhance their detection. We hypothesized that because all major mechanisms [16][17][18][19] (e.g., competition for charge 16 and space, 17 variation in solvent viscosity and surface tension due to the presence of matrix compounds, 18,19 etc.)…”

Extraordinary Transformations to Achieve the Synthesis of Remarkable Aromatic Compounds

“…[48] Although this chemistry was performed in a mass spectrometer, the potential to extend this to the micropreparative scale exists. [49] …”