Flexible access to 2,3,5,6-tetrasubstituted dehydropiperidines by Ni- or Co-catalyzed site-selective cross-coupling using Vilsmeier-Haack-derived α-chloro-β-formyltetrahydropyridines

A flexible and cost-effective method for the highly functional group-compatible and site-selective cross-coupling of readily affordable α-chloro-β-formyltetrahydropyridines has been developed, under nickel or cobalt catalysis, leading to the rapid synthesis of 2,3,5,6-tetrasubstituted dehydropiperidines bearing α-amino allylic stereocenters. Cobalt-catalyzed reductive cross-coupling of chloro enaminals with electronically-diverse bromostyrenes as coupling partners proceeds in good yields and with high E/Z selectivity to afford Diels-Alder-suitable cross-conjugated 1,3-dienes.     

Phenotyping Metastatic Brain Tumors Applying Spectrochemical Analyses: Segregation of Different Cancer Types

Metastatic brain tumors represent a significant proportion of tumors identified intraoperatively. A rapid diagnostic method, circumventing the need for histopathology studies, could prove clinically useful. As many spectroscopic studies have shown ability to differentitate between different tumor types, this technique was evaluated for use within metastatic brain tumors. Spectrochemical approaches [Raman and attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) spectroscopy] were applied to determine how readily they may identify the primary site for the metastatic tumor. Metastases were from primary adenocarcinomas of lung (n?=?7) and colorectum (n?=?7), and for comparison, metastatic melanoma (n?=?7). The objective was to determine if Raman or ATR-FTIR spectroscopy could delineate the origin of the primary tumor. The results demonstrate that there are marked similarities between the two adenocarcinoma groups and whilst Raman and ATR-FTIR can distinguish the three groups with limited success, classification accuracy is greatly improved when combining the adenocarcinoma groups. The use of such techniques in the clinical setting is more likely to be found intraoperatively, determining the presence of a tumor and suggesting the tumor class; however, traditional histopathology would still be needed to identify the primary origin of the tumor.     

Substituent effects on the amination of racemic allyl carbonates using commercially available chiral rhodium catalysts

In the presence of commercially available chiral rhodium catalysts, a competitive benzylamination of racemic allyl carbonates, substituted with p-X-Ph groups, shows that the reaction proceeds faster with substituents (X) that are more electron-withdrawing. Mechanistic implications of these results are discussed.     

An adhesive bond state classification method for a composite skin-to-spar joint using chaotic insonification

The combination of chaotically amplitude-modulated ultrasonic waves and time series prediction algorithms has shown the ability to locate and classify various bond state damage conditions of a composite bonded joint. This study examines the ability of a new two-part supervised learning classification scheme not only to classify disbond size but also to classify whether a bond for which there is no baseline data is undamaged or has some form of disbond. This classification is performed using data from a similarly configured composite bond for which baseline data are available. The test structures are analogous to a wing skin-to-spar bonded joint. An active excitation signal is imparted to the structure through a macro fiber composite (MFC) patch on one side of the bonded joint and sensed using an equivalent MFC patch on the opposite side of the joint. There is an MFC actuator/sensor pair for each bond condition to be identified. The classification approach compares features derived from an autoregressive (AR) model coefficient vector cross-assurance criterion.     

Analysis of the bonding in alkali-cation/Rg complexes (Rg = He–Xe) using a simple model potential

We have applied the model-potential analysis of Breckenridge and co-workers to the Alk⁺/Rg systems, where Alk is an alkali atom and Rg is a rare-gas atom. Three spectroscopic constants, R_e, D_e and ω_e, are employed to obtain the potential, with fitted parameters being the A and b repulsive Born–Mayer potential parameters, and the effective charge on the metal center, Z. From the analysis, it is concluded that all of these systems can be described in physical terms, with the calculated charge on the metal center being very close to 1.00. Interestingly the effective charge on the metal atom from such model-potential calculations is consistently very slightly greater than 1.00. We discuss and investigate several possible sources for this small anomaly, including a minor breakdown of the model at small internuclear separations, where the “lengths” of the induced multipoles become significant compared to the internuclear separation R. Despite this small breakdown, overall the model is remarkably successful in reproducing high-level ab initio curves for the titular complexes over wide ranges of internuclear distances.