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Prediction by 13C NMR of regioselectivity in 1,3‐dipolar cycloadditions of acridin‐9‐yl dipolarophiles 下载免费PDF全文
Mária Vilková Lucia Ungvarská Maľučká Ján Imrich 《Magnetic resonance in chemistry : MRC》2016,54(1):8-16
Strong correlation was found between 13C NMR chemical shifts of dipolarophilic CH?CH carbons and regioselectivity in 1,3‐dipolar cycloadditions of new acridin‐9‐yl dipolarophiles with stable benzonitrile oxides (BNO). Accordingly, two starting dipolarophiles, (acridin‐9‐yl)‐CH?CH‐R (R = COOCH3 or Ph), reacted with three BNOs (2,4,6‐trimethoxy, 2,4,6‐trimethyl, and 2,6‐dichloro) to give a mixture of two target isoxazoline regioisomers in which the acridine was bound either to isoxazoline C‐4 carbon (4‐Acr) or C‐5 one (5‐Acr). Methyl 3‐(acridin‐9‐yl)propenoate afforded major 4‐(acridin‐9‐yl)‐isoxazoline‐5‐carboxylates (4‐Acr) and minor 5‐(acridin‐9‐yl)‐4‐carboxylates (5‐Acr). 9‐(2‐Styryl)acridine regiospecifically afforded only 4‐Acr cycloadducts. The ratios of regioisomers were compared with analogous reactions of acridin‐4‐yl dipolarophiles. Regioselectivity was dependent on a polarity of the CH?CH bond, donor effects in BNO, and stabilization by stacking of aromatic substituents in the products. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
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Lucia Ungvarská Maľučká Mária Vilková Jozef Kožíšek Ján Imrich 《Magnetic resonance in chemistry : MRC》2016,54(1):17-27
Very strong proton deshielding was found in di/tri‐aromatic isoxazoline regioisomers prepared from acridin‐4‐yl dipolarophiles and stable benzonitrile oxides (BNO). Three alkenes, (acridin‐4‐yl)‐CH?CH‐R (R = COOCH3, Ph, and CONH2), reacted with three BNO dipoles (2,4,6‐trimethoxy, 2,4,6‐trimethyl, 2,6‐dichloro) to give pairs of target isoxazolines with acridine bound to C‐4 or C‐5 carbon of the isoxazoline (denoted as 4‐Acr or 5‐Acr). Regioselectivity was dependent on both the dipolarophile and dipole character. The ester and amide dipolarophile displayed variable regioselectivity in cycloadditions whereas the styrene one afforded prevailing 4‐Acr regioisomers. 2,4,6‐Trimethoxy‐BNO was most prone to form 5‐Acr isoxazolines while mesitonitrile oxide gave major 4‐Acr isoxazolines. Basic hydrolysis of the amide cycloadduct led to an unexpected isoxazolone product. The structure of the target compounds was studied by NMR, MS, and X‐ray crystallography. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
965.
Yves Achdou Fabio Camilli Alessandra Cutrì Nicoletta Tchou 《NoDEA : Nonlinear Differential Equations and Applications》2013,20(3):413-445
We consider continuous-state and continuous-time control problems where the admissible trajectories of the system are constrained to remain on a network. In our setting, the value function is continuous. We define a notion of constrained viscosity solution of Hamilton–Jacobi equations on the network and we study related comparison principles. Under suitable assumptions, we prove in particular that the value function is the unique constrained viscosity solution of the Hamilton–Jacobi equation on the network. 相似文献
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Prof. Dr. Bartolo Gabriele Dr. Raffaella Mancuso Dr. Lucia Veltri 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(15):5056-5094
Indanes and indenes are among the most important carbocycles. Many indane and indene derivatives have shown important pharmacological activities, and the indane and indene nuclei are structural motifs present in several natural products of biological relevance. In spite of their importance, only a few reviews on their preparation methods have appeared so far in the literature, the most recent ones being published about ten years ago. The present Review is aimed at filling this gap, presenting some of the most important and innovative approaches to indanes and indenes that have been published in the course of the last ten years (coverage: from 2005 to May, 2015). 相似文献
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Federico Magagna Lucia Valverde-Som Cristina Ruíz-Samblás Luis Cuadros-Rodríguez Stephen E. Reichenbach Carlo Bicchi Chiara Cordero 《Analytica chimica acta》2016
Comprehensive two-dimensional gas chromatography (GC × GC) is the most effective multidimensional separation technique for in-depth investigations of complex samples of volatiles (VOC) in food. However, each analytical run produces dense, multi-dimensional data, so elaboration and interpretation of chemical information is challenging. 相似文献
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Variable selection in high‐dimensional regression: a nonparametric procedure for business failure prediction 下载免费PDF全文
Alessandra Amendola Francesco Giordano Maria Lucia Parrella Marialuisa Restaino 《商业与工业应用随机模型》2017,33(4):355-368
Business failure prediction models are important in providing warning for preventing financial distress and giving stakeholders time to react in a timely manner to a crisis. The empirical approach to corporate distress analysis and forecasting has recently attracted new attention from financial institutions, academics, and practitioners. In fact, this field is as interesting today as it was in the 1930s, and over the last 80 years, a remarkable body of both theoretical and empirical studies on this topic has been published. Nevertheless, some issues are still under investigation, such as the selection of financial ratios to define business failure and the identification of an optimal subset of predictors. For this purpose, there exist a large number of methods that can be used, although their drawbacks are usually neglected in this context. Moreover, most variable selection procedures are based on some very strict assumptions (linearity and additivity) that make their application difficult in business failure prediction. This paper proposes to overcome these limits by selecting relevant variables using a nonparametric method named Rodeo that is consistent even when the aforementioned assumptions are not satisfied. We also compare Rodeo with two other variable selection methods (Lasso and Adaptive Lasso), and the empirical results demonstrate that our proposed procedure outperforms the others in terms of positive/negative predictive value and is able to capture the nonlinear effects of the selected variables. Copyright © 2017 John Wiley & Sons, Ltd. 相似文献