RESUMEN
We report a simple, efficient, and general method for the zinc-mediated regioselective cinnamylation of aldehydes and ketones under Barbier-type conditions in a one-pot synthesis affording the corresponding α-cinnamylated alcohols in moderate to excellent yields. Compared to the literature procedures, this approach is operationally simple, uses simple reactants, and provides direct access to linear α-cinnamylated alcohols with excellent regioselectivity. Experimental results suggest that the reactions proceed through the radical pathway. In addition, the reaction was found to be scalable to the gram-scale and the one-pot protocol is also applicable to less reactive esters leading to bishomoallylic alcohols which were valuable intermediates for desymmetrizing intramolecular Heck cyclization, allowing for the elaboration to functionalized building blocks.
RESUMEN
A convenient and highly α-regioselective strategy for the synthesis of 3-prenyl-3-hydroxy-2-oxindoles has been developed starting from isatins and prenylzinc with good to excellent yields. This protocol provides a straightforward and practical way to introduce an α-prenyl moiety into the C-3 position of isatins. The advantages of this reaction are use of the cheap and readily available reagents, operational simplicity, and wide substrate scope. Furthermore, this transformation was applied to the synthesis of several oxindole-containing natural products, which further demonstrated the synthetic utility of this methodology.
RESUMEN
An intramolecular [4 + 2] cycloaddition reaction of o-quinonemethides generated from salicylaldehydes and α-prenylated alcohols is described. In the presence of a catalytic amount of benzenesulfonic acid (BSA), the reaction proceeded smoothly in EtOH to afford furo[3,2-c]benzopyrans through a three-bond forming process in moderate to excellent yields with high diastereoselectivity. This reaction provides a simple and straightforward protocol to efficiently construct furo[3,2-c]benzopyran skeletons. A possible mechanism involving hemiacetal formation/hetero-Diels-Alder reaction is proposed to rationalize the observed results.
RESUMEN
PURPOSE: To propose and evaluate an automatic method of extracting parenchyma from a manually delineated whole liver for the R2* measurement of iron load. MATERIALS AND METHODS: In all, 108 transfusion-dependent patients with a wide range of hepatic iron content were scanned with a multiecho gradient-echo sequence. The R2* was measured by fitting the average signal of liver parenchyma, extracted by the proposed semiautomatic parenchyma extraction (SAPE), traditional manually delineated multiple regions-of-interest (mROIs), and T2* thresholding methods to the noise-corrected monoexponential model. The R2* measurement accuracy of the SAPE method was evaluated through simulation; the intra- and interobserver reproducibility of SAPE, mROI, and T2* thresholding were assessed from the in vivo data using coefficient of variation (CoV). RESULTS: In the simulation, the mean absolute percentage error of R2* measurement using SAPE was 0.23% (range 0.01%-1.09%). In vivo study, the CoVs of intra- and interobserver reproducibility were 0.83%, 1.39% for SAPE, 3.63%, 6.28% for mROI, and 1.62%, 2.66% for T2* thresholding, respectively. CONCLUSION: The SAPE method provides an accurate and reliable approach to assessing the overall hepatic iron content. The improved magnetic resonance imaging (MRI) R2* reproducibility using the SAPE method may lead to more accurate tissue characterization and increased diagnostic confidence.
Asunto(s)
Sobrecarga de Hierro/patología , Hepatopatías/patología , Hígado/patología , Imagen por Resonancia Magnética/métodos , Reconocimiento de Normas Patrones Automatizadas/métodos , Algoritmos , Biomarcadores/metabolismo , Femenino , Humanos , Aumento de la Imagen/métodos , Interpretación de Imagen Asistida por Computador/métodos , Hierro/metabolismo , Sobrecarga de Hierro/etiología , Sobrecarga de Hierro/metabolismo , Hígado/metabolismo , Hepatopatías/etiología , Masculino , Variaciones Dependientes del Observador , Reproducibilidad de los Resultados , Sensibilidad y Especificidad , Reacción a la Transfusión , Adulto JovenRESUMEN
OBJECTIVES: To evaluate the performance of region-of-interest (ROI)-based MRI R2* measurements by using the first-moment noise-corrected model (M(1)NCM) to correct the non-central Chi noise in magnitude images from phased arrays for hepatic iron content (HIC) assessment. METHODS: R2* values were quantified using the M(1)NCM model. Three approaches were employed to determine the representative R2*: fitting of the ROI-averaged signal (average-then-fit, ATF); outputting the median and mean of R2*s from the pixel-wise fitting of decay signals within the ROI (denoted as PWFmed and PWFmea, respectively). The accuracy and precision of the three approaches were evaluated on synthesized data. The agreement among these approaches and their intra- and inter-observer reproducibility were assessed on 105 thalassaemia major patients. RESULTS: Simulations showed that ATF consistently yielded the highest accuracy and precision at varying noise levels. By contrast, PWFmed and PWFmea slightly and significantly overestimated high R2* at poor signal-to-noise ratios, respectively. Patient study showed that ATF agreed well with PWFmed, whereas PWFmea produced high R2* measurements for patients with severe HIC. No significant difference was observed in the reproducibility of the three approaches. CONCLUSIONS: PWFmea tends to overestimate high R2*, whereas ATF and PWFmed can produce more accurate R2* measurements for HIC assessment.