RESUMEN
We report for the first time that the imidate radical can be efficiently added to glycals to generate glycosyl radicals, based on which a general, toxic-reagent-free synthesis of C-glycosides of 2-deoxy-2-amino sugars has been developed. Complementary to previous strategies, the reaction is 1,2-trans-stereoselective and could use aryl alkenes as substrates. The late-stage functionalization and density functional theory calculations are reported.
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Alquenos/química , Glicósidos/síntesis química , Glicósidos/química , Indicadores y Reactivos/química , Estructura Molecular , EstereoisomerismoRESUMEN
Stereoselectively-fluorinated analogs of pipecolic acid have been investigated through a combined theoretical and experimental approach. Three of the four possible diastereoisomers of 4,5-difluoropipecolic acid were successfully synthesized via deoxyfluorination chemistry, navigating a complex reaction network that included neighboring group participation, rearrangement, and elimination pathways. A DFT-based conformational study, supported by NMR J-based analysis, revealed that the different diastereoisomers of 4,5-difluoropipecolic acid preferentially adopt different puckers of the six-membered ring. These findings could have future relevance for the conformational control of biologically active peptides.
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Ácidos PipecólicosRESUMEN
The aim of this meta-analysis was to evaluate the diagnostic value of 3D time-of-flight magnetic resonance angiography (3D-TOF-MRA) in trigeminal neuralgia (TN). Relevant studies were identified by computerized database searches supplemented by manual search strategies. The studies were included in accordance with stringent inclusion and exclusion criteria. Following a multistep screening process, high quality studies related to the diagnostic value of 3D-TOF-MRA in TN were selected for meta-analysis. Statistical analyses were conducted using Statistical Analysis Software (version 8.2; SAS Institute, Cary, NC, USA) and Meta Disc (version 1.4; Unit of Clinical Biostatistics, Ramon y Cajal Hospital, Madrid, Spain). For the present meta-analysis, we initially retrieved 95 studies from database searches. A total of 13 studies were eventually enrolled containing a combined total of 1084 TN patients. The meta-analysis results demonstrated that the sensitivity and specificity of the diagnostic value of 3D-TOF-MRA in TN were 95% (95% confidence interval [CI] 0.93-0.96) and 77% (95% CI 0.66-0.86), respectively. The pooled positive likelihood ratio and negative likelihood ratio were 2.72 (95% CI 1.81-4.09) and 0.08 (95% CI 0.06-0.12), respectively. The pooled diagnostic odds ratio of 3D-TOF-MRA in TN was 52.92 (95% CI 26.39-106.11), and the corresponding area under the curve in the summary receiver operating characteristic curve based on the 3D-TOF-MRA diagnostic image of observers was 0.9695 (standard error 0.0165). Our results suggest that 3D-TOF-MRA has excellent sensitivity and specificity as a diagnostic tool for TN, and that it can accurately identify neurovascular compression in TN patients.