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221.
Jana L. Markley Tyler L. Morse Nigam P. Rath Timothy A. Wencewicz 《Tetrahedron》2018,74(22):2743-2753
A photochemical approach to 3-phenyl-3-hydroxy-β-lactams (3-HβLs) is reported. Irradiation of aryl-β-ketoformamides with a UV light band centered at 300?nm provides the corresponding 3-aryl-3-HβLs with good conversion. The scope of the photocyclization is explored with an electronically diverse panel of substrates that provides mechanistic insight supporting a Norrish-Yang type II cyclization. A flexible synthetic route to phenyl-β-ketoformamides, followed by photoirradiation, allows for efficient incorporation of the β-lactam pharmacophore into aromatic organic scaffolds. Taken collectively, the improved and optimized synthetic route to provide both β-ketoformamides and 3-HβLs—in combination with the expanded analysis of substrate scope and limitations—reported herein will serve as a necessary reference for the direct, atom-economical, radical-mediated installation of 3-HβL scaffolds en route to the generation of other biologically active small molecules. 相似文献
222.
Lohier JF Foucoin F Jaffrès PA Garcia JI Sopková-de Oliveira Santos J Perrio S Metzner P 《Organic letters》2008,10(6):1271-1274
A straightforward and high-yielding access to various [2.2]paracyclophanes possessing a sulfur-based functional group is reported, the key step being a SEAr reaction mediated by a sulfonium salt. The versatility of the methodology was exemplified by an original application in sulfenate salt chemistry, from which a remarkable chirality transfer was observed. 相似文献
223.
The first total synthesis of Ciliatamides A-C was completed, leading to a revision of the reported stereochemistry from (S,S) to the (R,R) enantiomers. Due to the expedited route, a library of over 50 unnatural ciliatamide analogs was also prepared. 相似文献
224.
The mechanism and the rate of hydrogen bond-breaking in the hydration layer surrounding an aqueous protein are important ingredients required to understand the various aspects of protein dynamics, its function, and stability. Here, we use computer simulation and a time correlation function technique to understand these aspects in the hydration layer of lysozyme. Water molecules in the layer are found to exhibit three distinct bond-breaking mechanisms. A large angle orientational jump of the donor water molecule is common among all of them. In the most common ( approximately 80%) bond-breaking event in the layer, the new acceptor water molecule comes from the first coordination shell (initially within 3.5 A of the donor), and the old acceptor water molecule remains within the first coordination shell, even after the bond-breaking. This is in contrast to that in bulk water, in which both of the acceptor molecules involve the second coordination shell. Additionally, the motion of the incoming and the outgoing acceptor molecules involved is not diffusive in the hydration layer, in contrast to their observed diffusive motion in the bulk. The difference in rotational dynamics between the bulk and the hydration layer water molecules is clearly manifested in the calculated time-dependent angular van Hove self-correlation function ( G(theta, t)) which has a pronounced two-peak structure in the layer, and this can be traced to the constrained translational motion in the layer. The longevity of the surrounding hydrogen bond network is found to be significantly enhanced near a hydrophilic residue. 相似文献
225.
Precechtelová J Padrta P Munzarová ML Sklenár V 《The journal of physical chemistry. B》2008,112(11):3470-3478
31P chemical shift anisotropy (CSA) tensors have been calculated for a set of selected DNA and RNA backbone conformations using density functional theory. The set includes canonical A-RNA, A-DNA, BI-DNA, BII-DNA, ZI-DNA, and ZII-DNA as well as four A-RNA-type, seven non-A-RNA-type, and three non-canonical DNA conformations. Hexahydrated dimethyl phosphate has been employed as a model. The 31P chemical shift tensors obtained are discussed in terms of similarities in the behavior observed for gauche-gauche (gg) and gauche-trans (gt) conformations around the P-O bonds. We show that torsion angles alpha and zeta are major determinants of the isotropic chemical shift deltaiso and of the deltaCSA11 component of the traceless chemical shift tensor, which is revealed in separate ranges of both deltaiso and deltaCSA11 for gg- and gt-conformers, respectively. A clear distinction between the two conformation types has not been found for the deltaCSA22 and deltaCSA33 components, which is attributed to their different directional properties. The 31P CSA tensors exhibit considerable variations resulting in large spans of approximately 16 ppm for deltaCSA11 and approximately 22 ppm for deltaCSA22 and deltaCSA33. We examine the consequences of the CSA variations for predicting the chemical shift changes upon partial alignment deltacsa and for the values of CSA order parameters extracted from the analysis of 31P NMR relaxation data. The theoretical 31P CSA tensors as well as the experimental 31P CSA tensor of barium diethyl phosphate (BDEP) are used to calculate deltacsa for two eclipsed orientations of the CSA and molecular alignment tensors. Percentage differences between the CSA order parameters obtained using the theoretical 31P CSA tensors and the experimental 31P CSA tensor of BDEP, respectively, are also determined. 相似文献
226.
A new application is described of a dual photometric/contactless conductivity detector to CE determination of incompletely separated compounds. These compounds are differentiated when one of them provides signals in both the cells of the detector, whereas the other yields a signal in only one cell. The technique has been applied to determination of proline and tyrosine in a dietary supplement. 相似文献
227.
The prediction of soil metal phytoavailability using the chemical extractions is a conventional approach routinely used in soil testing. The adequacy of such soil tests for this purpose is commonly assessed through a comparison of extraction results with metal contents in relevant plants. In this work, the fractions of selected risk metals (Al, As, Cd, Cu, Fe, Mn, Ni, Pb, Zn) that can be taken up by various plants were obtained by optimized BCR (Community Bureau of Reference) three-step sequential extraction procedure (SEP) and by single 0.5 mol L(-1) HCl extraction. These procedures were validated using five soil and sediment reference materials (SRM 2710, SRM 2711, CRM 483, CRM 701, SRM RTH 912) and applied to significantly different acidified soils for the fractionation of studied metals. The new indicative values of Al, Cd, Cu, Fe, Mn, P, Pb and Zn fractional concentrations for these reference materials were obtained by the dilute HCl single extraction. The influence of various soil genesis, content of essential elements (Ca, Mg, K, P) and different anthropogenic sources of acidification on extraction yields of individual risk metal fractions was investigated. The concentrations of studied elements were determined by atomic spectrometry methods (flame, graphite furnace and hydride generation atomic absorption spectrometry and inductively coupled plasma optical emission spectrometry). It can be concluded that the data of extraction yields from first BCR SEP acid extractable step and soil-plant transfer coefficients can be applied to the prediction of qualitative mobility of selected risk metals in different soil systems. 相似文献
228.
Daniel Moser Dr. Kalipada Jana Prof. Dr. Christof Sparr 《Angewandte Chemie (International ed. in English)》2023,62(39):e202309053
Herein, we describe the feasibility of atroposelective PIII/PV=O redox organocatalysis by the Staudinger–aza-Wittig reaction. The formation of isoquinoline heterocycles thereby enables the synthesis of a broad range of valuable atropisomers under mild conditions with enantioselectivities of up to 98 : 2 e.r. Readily prepared azido cinnamate substrates convert in high yield with stereocontrol by a chiral phosphine catalyst, which is regenerated using a silane reductant under Brønsted acid co-catalysis. The reaction provides access to diversified aryl isoquinolines, as well as benzoisoquinoline and naphthyridine atropisomers. The products are expeditiously transformed into N-oxides, naphthol and triaryl phosphine variants of prevalent catalysts and ligands. With dinitrogen release and aromatization as ideal driving forces, it is anticipated that atroposelective redox organocatalysis provides access to a multitude of aromatic heterocycles with precise control over their configuration. 相似文献
229.
Verbitski SM Gourdin GT Ikenouye LM McChesney JD Hildreth J 《Journal of AOAC International》2008,91(2):268-275
Actaea racemosa L. (black cohosh; syn. Cimicifuga racemosa L. Nutt.) is a native North American perennial whose root and rhizome preparations are commercially available as phytomedicines and dietary supplements, primarily for management of menopausal symptoms. Despite its wide use, methods that accurately identify processed A. racemosa are not well established; product adulteration remains a concern. Because of its similar appearance and growing locales, A. racemosa has been unintentionally mixed with other species of the genus, such as Actaea pachypoda Ell. (white cohosh) and more commonly Actaea podocarpa DC. (yellow cohosh). The genus Actaea also has 23 temperate species with numerous common names, which can also contribute to the misidentification of plant material. Consequently, a variety of Actaea spp. are common adulterants of commercially available black cohosh preparations. Thin-layer chromatography (TLC) and combined TLC-bioluminescence (Bioluminex) are efficient, economical, and effective techniques which provide characteristic patterns and toxicity profiles for each plant species. These data indicate that common black cohosh adulterants, such as yellow cohosh, can be differentiated from black cohosh by TLC and TLC-bioluminescence. This study also showed that unknown contaminants that were not detected using standard A. racemosa identity techniques were readily detected by TLC and TLC-bioluminescence. 相似文献
230.