Investigation of the Deprotonative Generation and Borylation of Diamine-Ligated α-Lithiated Carbamates and Benzoates by in situ IR spectroscopy

Diamine-mediated α-deprotonation of <i>O</i>-alkyl carbamates or benzoates with alkyllithium reagents, trapping of the carbanion with organoboron compounds, and 1,2-metalate rearrangement of the resulting boronate complex are the primary steps by which organoboron compounds can be stereoselectively homologated. Although the final step can be easily monitored by ¹¹B NMR spectroscopy, the first two steps, which are typically carried out at cryogenic temperatures, are less well understood owing to the requirement for specialized analytical techniques. Investigation of these steps by in situ IR spectroscopy has provided invaluable data for optimizing the homologation reactions of organoboron compounds. Although the deprotonation of benzoates in noncoordinating solvents is faster than that in ethereal solvents, the deprotonation of carbamates shows the opposite trend, a difference that has its origin in the propensity of carbamates to form inactive parasitic complexes with the diamine-ligated alkyllithium reagent. Borylation of bulky diamine-ligated lithiated species in toluene is extremely slow, owing to the requirement for initial complexation of the oxygen atoms of the diol ligand on boron with the lithium ion prior to boron–lithium exchange. However, ethereal solvent, or very small amounts of THF, facilitate precomplexation through initial displacement of the bulky diamines coordinated to the lithium ion. Comparison of the carbonyl stretching frequencies of boronates derived from pinacol boronic esters with those derived from trialkylboranes suggests that the displaced lithium ion is residing on the pinacol oxygen atoms and the benzoate/carbamate carbonyl group, respectively, explaining, at least in part, the faster 1,2-metalate rearrangements of boronates derived from the trialkylboranes

The dayside high-latitude trough under quiet geomagnetic conditions: Radio tomography and the CTIP model

The dayside high-latitude trough is a persistent feature of the post-noon wintertime auroral ionosphere. Radio tomography observations have been used to map its location and latitudinal structure under quiet geomagnetic conditions (&lt;i&gt;K&lt;sub&gt;p&lt;/sub&gt;&lt;/i&gt;&amp;le;2) near winter solstice. The trough is also a clear feature in the ion density distribution of the Coupled Thermosphere-Ionosphere-Plasmasphere model (CTIP) under similar geophysical conditions. Comparisons of the measured and modelled distributions show that the plasma production equatorward of the trough is mainly controlled by solar radiation, but there are also other processes maintaining the equatorward trough-wall that are open to debate. The poleward trough-wall is produced by particle precipitation, but the densities are significantly overestimated by the model. At the trough minimum the observed densities are consistent with low nighttime densities convecting sunward to displace the higher daytime densities, but this is not borne out by the CTIP model. The study shows the potential of combining radio tomography and modelling to interpret the balance of the physical processes responsible for large-scale structuring of the high-latitude ionosphere, and highlights the role of tomographic imaging in validating and developing physical models