Selective access to dihydrophenanthridines and phenanthridinones via cyclisation of aryl amines onto N-tethered arynes.

5,6-Dihydrophenanthridines are prepared from aryl amines via intramolecular addition to N-tethered arynes under mild conditions. A new o-silylaryl triflate precursor was developed to increase reactivity and enable electron-rich and electron-poor aryl amines to undergo cyclisation. A complete switch in product selectivity occurs when the reaction is conducted in air, affording the corresponding phenanthridin-6(5H)-one as the sole product under otherwise identical reaction conditions.

A simple Hückel model-driven strategy to overcome electronic barriers to retro-Brook silylation relevant to aryne and bisaryne precursor synthesis.

ortho-Silylaryl triflate precursors (oSATs) have been responsible for many recent advances in aryne chemistry and are most commonly accessed from the corresponding 2-bromophenol. A retro-Brook O- to C-silyl transfer is a key step in this synthesis but not all aromatic species are amenable to the transformation, with no functionalized bisbenzyne oSATs reported. Simple Hückel models are presented which show that the calculated aromaticity at the brominated position is an accurate predictor of successful retro-Brook reaction, validated synthetically by a new success and a predicted failure. From this, the synthesis of a novel difunctionalized bisaryne precursor has been tested, requiring different approaches to install the two C-silyl groups. The first successful use of a disubstituted o-silylaryl sulfonate bisbenzyne precursor in Diels-Alder reactions is then shown.

[High resolution reconstruction of PET images using the iterative OSEM algorithm]. / Auflösungsverbesserende Rekonstruktion von PET-Bildern mit dem iterativen OSEM-Algorithmus.

AIM: Improvement of the spatial resolution in positron emission tomography (PET) by incorporation of the image-forming characteristics of the scanner into the process of iterative image reconstruction. METHODS: All measurements were performed at the whole-body PET system ECAT EXACT HR(+) in 3D mode. The acquired 3D sinograms were sorted into 2D sinograms by means of the Fourier rebinning (FORE) algorithm, which allows the usage of 2D algorithms for image reconstruction. The scanner characteristics were described by a spatially variant line-spread function (LSF), which was determined from activated copper-64 line sources. This information was used to model the physical degradation processes in PET measurements during the course of 2D image reconstruction with the iterative OSEM algorithm. To assess the performance of the high-resolution OSEM algorithm, phantom measurements performed at a cylinder phantom, the hotspot Jaszczack phantom, and the 3D Hoffmann brain phantom as well as different patient examinations were analyzed. RESULTS: Scanner characteristics could be described by a Gaussian-shaped LSF with a full-width at half-maximum increasing from 4.8 mm at the center to 5.5 mm at a radial distance of 10.5 cm. Incorporation of the LSF into the iteration formula resulted in a markedly improved resolution of 3.0 and 3.5 mm, respectively. The evaluation of phantom and patient studies showed that the high-resolution OSEM algorithm not only lead to a better contrast resolution in the reconstructed activity distributions but also to an improved accuracy in the quantification of activity concentrations in small structures without leading to an amplification of image noise or even the occurrence of image artifacts. CONCLUSION: The spatial and contrast resolution of PET scans can markedly be improved by the presented image restauration algorithm, which is of special interest for the examination of both patients with brain disorders and small animals.