Recent advances/contributions in the Suzuki–Miyaura reaction

Since the original reports of Suzuki-Miyaura on the coupling of vinyl or aryl boronic acids with vinyl or aryl halides a remarkable number of publications have either developed or applied this methodology in both an academic and industrial setting. This review covers recent developments in the area, focusing on new methodology, mechanistic implications and applications in medicinal, process and materials chemistry

Perpetual Care: A Sustainable Approach to Restoring the Lost Landscapes of America\u27s Rural Cemeteries

During the mid 19th century burial practices in America evolved drastically with the creation of “rural” cemeteries. These burial grounds became incredibly popular didactic landscapes that were physical manifestations of contemporary Victorian social forces. Many of these historic landscapes are in need of conservation and restoration in order to preserve what remains. This thesis project lays out the significance of these sites, and provides a guide to restoring the character defining features of these cemeteries

New systems for catalytic asymmetric epoxidation

This thesis describes the catalytic asymmetric epoxidation of olefins mediated by oxaziridinium salts. The introduction highlights some of the most successful methods for preparing chiral oxiranes and hints at the synthetic utility of this versatile molecule. The second chapter is dedicated to our efforts to synthesize chiral iminium salts as catalysts for asymmetric epoxidation. The first part of this chapter describes previous Page group findings and leads on to the current author's efforts in this area. Initial results from modified amino acids, cyclo-condensed to form dihydroisoquinolinium salts, showed that an aromatic unit at C4 of our catalysts was vital for asymmetric induction. Following this, several catalysts substituted at the 4-position of the aromatic functionality were tested, and found to be effective mediators for asymmetric epoxidation. Triphenylethylene was epoxidized with up to 71% ee when using oxone as the stochieometric oxidant. [Continues.

Searches for new physics with boosted top quarks in the MadAnalysis 5 and Rivet frameworks

High-momentum top quarks are a natural physical system in collider experiments for testing models of new physics, and jet substructure methods are key both to exploiting their largest decay mode and to assuaging resolution difficulties as the boosted system becomes increasingly collimated in the detector. To be used in new-physics interpretation studies, it is crucial that related methods get implemented in analysis frameworks allowing for the reinterpretation of the results of the LHC such as MadAnalysis 5 and Rivet. We describe the implementation of the HEPTopTagger algorithm in these two frameworks, and we exemplify the usage of the resulting functionalities to explore the sensitivity of boosted top reconstruction performance to new physics contributions from the Standard Model Effective Field Theory. The results of this study lead to important conclusions about the implicit assumption of Standard-Model-like top-quark decays in associated collider analyses, and for the prospects to constrain the Standard Model Effective Field Theory via kinematic observables built from boosted semi-leptonic $t\bar{t}$ events selected using HEPTopTagger.Comment: 26 pages, 5 figure

Thiadiazolidine 1-oxide systems for phosphine-free palladium-mediated catalysis

We herein report several highly active catalyst systems with thiadiazolidine 1-oxides as ligands for palladium in the Mizoroki–Heck reaction. Excellent yields of stilbenes derived from aryl iodides and bromides have been achieved using as little as 0.00002 mol % catalyst. The ligand/palladium system can be stored as a stock solution open to air at room temperature with no observable loss of activity for a period of several months

Impaired myocardial relaxation with exercise determines peak aerobic exercise capacity in heart failure with preserved ejection fraction

Background Heart failure with preserved ejection fraction (HFpEF) is a clinical syndrome characterized by impaired exercise capacity due to shortness of breath and/or fatigue. Assessment of diastolic dysfunction at rest and with exercise may provide insight into the pathophysiology of exercise intolerance in HFpEF. Aims To measure echocardio-Doppler-derived parameters of diastolic function as they relate to various indices of aerobic exercise capacity in HFpEF. Methods We selected 16 subjects with clinically stable HFpEF, no evidence of volume overload, but impaired functional capacity by cardiopulmonary exercise testing [peak oxygen consumption (VO2)]. We measured the transmitral E and A flow velocities, E/A ratio, and E deceleration time (DT) and tissue Doppler E′ velocity. We also indexed the E′ to the DT, as additional measure of impaired relaxation (E′DT), and calculated the diastolic functional reserve index (DFRI), as the product of E′ at rest and change in E′ with exercise. Results E′ velocity, at rest and peak exercise, as well as the DFRI positively correlated with peak VO2, whereas DT, E′DT, and E/E′ with exercise inversely correlated with peak VO2. Of note, the E′DT at rest also significantly predicted E′ velocity at peak exercise (R = +0.81, P \u3c 0.001). Exercise E′ was the only independent predictor of peak VO2 at multivariable analysis (R = +0.67, P = 0.005). Conclusions The E′ velocity at peak exercise is a strong and independent predictor of aerobic exercise capacity as measured by peak VO2 in patients with HFpEF, providing the link between abnormal myocardial relaxation with exercise and impaired aerobic exercise capacity in HFpEF

A catalytic, mild and efficient protocol for the C-3 aerial hydroxylation of oxindoles

A mild, high yielding approach to C-3 hydroxylated oxindoles using catalytic quantities of tetrabutylammonium fluoride and air as the stoicheiometric oxidant is reported over a wide range of substitution patterns

Plasmas for organic synthesis and chemical probes for plasma diagnostics

Although organic chemistry plays a critical role in many plasma applications, there is room for further cross-fertilization between the two disciplines. Here we explore two possible avenues: (1) plasma physics as a new tool for the organic chemist and (2) organic compounds as diagnostics for the plasma physicist

Comparative study of chemical probes for ozone detection

Plasma composition is typically studied by absorption and emission spectroscopy, mass spectrometry and computational studies. While these techniques provide valuable information about the chemical species in the gas phase, in many applications it is desirable to have a direct measurement of the dose of chemical species delivered to a particular target. For this purpose, chemical probes are particularly interesting as they can provide an inexpensive means for determining the dose of a particular compound. A number of chemical probes have recently been used by the plasma community, particularly those working in plasma medicine and with plasmas interacting with liquids. Generally, however, these probes were not initially intended for use in plasma environments and therefore, it is important to assess their suitability and identify any selectivity issue that could affect the correct interpretation of the measurements. Here, we report on a comparative study of three chemical probes aimed at the quantitative detection of ozone (Table 1): Indigo Carmine and two DCF-derived fluorescent probes