Angew Chem Int Ed Engl
December 2024
Organofluorine compounds are vital across multiple sectors, hence highly selective methods to install fluorine are of considerable importance. The deoxyfluorination of alcohols is a key approach to prepare organofluorine compounds, however, a highly secondary (2°)-selective deoxyfluorination of alcohols has not been realized to date. Herein, we report that borane-mediated deoxyfluorination results in high 2°-selectivity in inter- and intra-molecular competition reactions versus primary (1°), tertiary (3°) and even benzylic (Bn) alcohols.
View Article and Find Full Text PDFOrganic ultralong room temperature phosphorescence (RTP), or organic afterglow, is a unique phenomenon, gaining widespread attention due to its far-reaching application potential and fundamental interest. Here, two laterally expanded 9,10-dimesityl-dihydro-9,10-diboraanthracene (DBA) derivatives are demonstrated as excellent afterglow materials for red and blue-green light emission, which is traced back to persistent thermally activated delayed fluorescence and RTP. The lateral substitution of polycyclic DBA scaffold, together with weak transversal electron-donating mesityl groups, ensures the optimal molecular properties for (reverse) intersystem crossing and long-lived triplet states in a rigid poly(methyl methacrylate) matrix.
View Article and Find Full Text PDFDespite the general high fluorophilicity of boron, organoboranes such as BEt and 3,5-(CF)CH-BPin are shown herein for the first time, to our knowledge, to be effective (solid to solution) phase-transfer catalysts for the fluorination of certain organohalides with CsF. Significant (up to 30% e.e.
View Article and Find Full Text PDFHelicenes are chiral polycyclic aromatic hydrocarbons (PAHs) of significant interest, in supramolecular chemistry, materials science and asymmetric catalysis. Herein an enhanced N-directed electrophilic C-H borylation methodology has been developed that provides access to azaborine containing helicenes (BN-helicenes). This borylation process proceeds protonation of an aminoborane with bistriflimidic acid.
View Article and Find Full Text PDFHaloboration, the addition of B-X (X = Cl, Br, I) across an unsaturated moiety , C[double bond, length as m-dash]Y or C[triple bond, length as m-dash]Y (Y = C, N, ), is dramatically less utilised than the ubiquitous hydroboration reaction. However, haloboration of alkynes in particular is a useful tool to access ambiphilic 1,2-disubstituted alkenes. The stereochemical outcome of the reaction is easily controlled and the resulting products have proven to be valuable building blocks in organic synthesis and materials chemistry.
View Article and Find Full Text PDFThe addition of 2 eq. of MesLi to the biphenylene-containing 9,10-dihydro-9,10-diboraanthracene (DBA) 2 results in the formation of the corresponding oxaboraphenanthrene 3 after column chromatography under ambient conditions. In the initial step, the anionic B-Mes monoadduct of 2 is generated, which eliminates a formal [MesB:] ion with concomitant C-C-bond formation (room temperature, 18 h).
View Article and Find Full Text PDFBackground: An objective way to qualify the effect of radiotherapy (RT) on lung tissue is the analysis of CT scans after RT. In this analysis we focused on the changes in Hounsfield units (ΔHU) and the correlation with the corresponding radiation dose after RT.
Methods: Pre- and post-RT CT scans were matched and ΔHU was calculated using customized research software.
Doubly boron-doped anthracenes and pentacenes have been longitudinally and laterally expanded through annulation of thiophene or benzene rings. The obtained series of closely related compounds allowed an assessment of key structure-property relationships with a focus on optoelectronic characteristics. Most of the products are benchtop-stable blue emitters and capable of accepting two electrons in a reversible manner.
View Article and Find Full Text PDFOptimized syntheses of 6,13-dimesityl-6,13-dihydro-6,13-diborapentacene (DBP) and a related compound (DBI) featuring two biphenylene-2,3-diyl units in place of naphthalene-2,3-diyl moieties are reported. Striking differences between the optoelectronic properties of DBP and DBI have been experimentally observed, and explained by quantum chemical calculations. DBP is a member of the oligoacene family, DBI is a linear [N]phenylene derivative.
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