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Eleven quinolizidine-based alkaloids (QBAs) were synthesized in a straightforward, flexible, and stereoselective manner. As the key step, which was run on a multi-gram scale, the organocatalytic, highly enantio- and diastereoselective vinylogous Mukaiyama-Mannich reaction was used furnishing highly functionalized products carrying already two stereogenic centers. The quinolizidinone core was subsequently assembled through cyclization reactions of both ester groups with the amine moiety. Whereas the absolute configuration of the bridgehead carbon atom and the adjacent chiral center were established in the initial vinylogous Mannich reaction, the stereogenic center at the 4-position was introduced in the last step through amide activation and organometallic addition exploiting stereochemical control from the substrate. Taking advantage of this unified strategy, simple as well as more complex alkaloids were accessible in good overall yields and with high stereoselectivity. Some of the QBAs were synthesized for the first time and this study could help to assign their absolute and relative configurations. [ABSTRACT FROM AUTHOR]

Background: Posttraumatic maltorsion and implant failure after closed reduction of proximal femoral fractures remain a cause of concern. Although the reproducibility of torsion measuring techniques on CT for femoral shaft fractures has been thoroughly analyzed, little is known about the trochanteric fractures. Apart from the well-known CT limitations, posttraumatic alteration of bony landmarks makes torsional assessment even more challenging. Main goal of this study was to examine the reliability of different CT techniques on trochanteric femoral fractures after closed nail fixation. Secondary goal was to see whether the measurements within the examined population were influenced by the fracture type and patient age or BMI.Methods: 20 cases (AO.31-A1 or -A2) were retrospectively examined. Six established CT techniques for torsional assessment were performed from three different investigators twice at different time points. The intraclass correlation coefficient (ICC for 95% CI) was used to analyze the interobserver and intraobserver reliability.Results: The Hernandez method (0.986) followed by the Jend method (0.982) by a mean difference of <1° showed the highest reliability. Although increasing fracture complexity from A1 to A2 led to an overall worsening of the measurement precision, the Hernandez and Jend techniques revealed a very good consistency. Within the examined population, age and BMI had no impact on the precision of the measurements.Conclusions: The Hernandez and Jend methods represent reliable alternatives for torsional assessment of trochanteric femur fractures treated with closed nail fixation when compared to the other measurement techniques here involved. Documentation of the torsion measuring method used in each case constitutes an essential element of the radiological reports. [ABSTRACT FROM AUTHOR]

Sixteen indolizidine-based alkaloids (IBAs) that were isolated as poison constituents of the skin of frogs were synthesized in a highly flexible and stereoselective manner. As a key step, a three-component, organocatalytic, highly enantio- and diastereoselective vinylogous Mukaiyama-Mannich reaction was employed furnishing optically highly enriched butyrolactams as central intermediates on a multigram scale. The attached six-membered ring was constructed through cyclization of the pendant enoate moiety onto the pyrrolidine ring. The absolute configuration of the bridgehead chiral center and the adjacent 8-position was established in the initial vinylogous Mannich reaction, whereas the 3- and 5-substituents were introduced through organometallic addition at a late stage of the synthesis with full stereochemical control from the substrate. With this strategy, simple as well as even more complex alkaloids were accessible in good overall yields as single stereoisomers. These syntheses also served to establish the absolute and relative configuration of those IBAs that had never been synthesized before., (Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)