A novel Cu-catalyzed diastereo- and enantioselective desymmetrization of cyclopropenes to afford nonracemic cyclopropylboronates is described. Trapping the cyclopropylcopper intermediate with electrophilic amines allows for the synthesis of cyclopropylaminoboronic esters and demonstrates the potential of the approach for the synthesis of functionalized cyclopropanes.
In this report, we establish that
DM-Segphos copper(I) complexes
are efficient catalysts for the enantioselective borylation of para-quinone methides. This method provides straightforward
access to chiral monobenzylic and dibenzylic boronic esters, with
enantiomeric ratios up to 96:4, using a commercially available chiral
phosphine. Standard manipulations of the C–B bond afford a
variety of chiral diaryl derivatives.
An efficient and general copper(i)-catalyzed silylation of p-quinone-methides is described. Non-symmetric dibenzylic silanes are obtained in high yields under mild reaction conditions. These compounds can be used as bench-stable benzylic carbanion precursors.
In this report, the enantioselective, copper-catalyzed borylation of β-amidoacrylates is disclosed. A broad variety of biologically important α-aminoboronates has been prepared with consistently high levels of enantiocontrol using an inexpensive copper catalyst and a commercially available chiral ligand. The method can be applied to the synthesis of novel boron-containing dipeptides and hemiboronates.
Introduction: The domestic and peridomestic presence of Triatoma infestans depends on several factors, such as human behavior, vector behavior, ecology, and the environment. Methods: This work was conducted in 139 domiciliary units, where triatomines were captured and risk factors in domiciles and peridomicilies were recorded. Household dwellers were interviewed to obtain information about practices regarding this disease and entomological indicators were calculated. Results: Infestation indices were 59.7% for house compounds, 4.3% for domestic areas and 58.3% for the peridomestic areas. Intradomicile infestation was significantly associated with housing characteristics. The presence of chicken coops in peridomicilies was associated with an increased risk of infestation. Of the respondents, 80% did not recognize the importance of the peridomiciliary structures for triatomine control and had infested peridomicilies. Conclusions: The results show the importance of peridomiciles as refuge sites for Triatominae bugs; however, household dwellers do not perceive peridomiciles as areas that favor the presence of vectors. Actions for raising awareness about factors that favor the presence of triatomines are needed to improve the conditions of peridomiciliary environments.
Chimerism is defined as the presence in a subject of more than one stable and genetically distinct cell line; cases reported so far include both patients with ambiguous genitalia and healthy subjects. The biological mechanisms, which may give origin to chimeras, are complex, and can be understood by analyzing DNA samples of the patients and their parents using molecular techniques. The objective of this study is to identify the mechanism of origin for the 2 cases we report. The first patient is a phenotipically normal girl with normal (external and internal) genitalia; the second patient had ambiguous genitalia and underwent surgery. DNA was purified from blood samples and, limited to Patient 1, from a sample of biliary cyst. Short tandem repeat polymorphisms were analyzed in order to identify the relative parental contribution to the patients. Molecular analyses carried out on the first patient are not fully informative because of two possible explanations (<i>i.e. </i>parthenogenetic and andrognetic chimera), while in the second case the presence of four alleles at some markers allowed us to identify a tetragametic chimera originnated from the fusion of two distinct embryos. Studies carried on one single tissue may not always be conclusive as they do not allow the precise identification of the mechanism of origin. In these cases, studies on more tissues are strongly suggested
Studying the bioavailability of sediment-bound contaminants is complicated by many reasons, such as the variable composition of the particles, their temporal variations, the low levels of contaminant concentrations, their partitioning between diverse aqueous and particulate phases, and the variety of uptake routes that may involved with the biota. Therefore, simple and innovative methodologies should be tested as analogues for natural sediments. Among them, a diverse selection of artificial particles with well-defined surface properties, in the presence and absence of commercially available humic acids, has been proposed and used to investigate the bioavailability of several organic pollutants. For this work, this model was applied to investigate the uptake and accumulation of cadmium by the freshwater oligochaete Lumbriculus variegatus. The results showed that the uptake of the metal depended on the free dissolved Cd(II) species, while the contribution from the particles was negligible. Thus, the extent of cadmium bioaccumulated from each test system could be predicted as a function of the rate of absorption of the free dissolved Cd(II) species. These species were calculated either from the particle-water partition coefficients, or by using the MINEQL+ computer program. In general, the estimated accumulation levels were in good agreement with the experimental results.
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