Phosphine-Catalyzed Formation of Carbon-Sulfur Bonds: Catalytic Asymmetric Synthesis of gamma-Thioesters

Supporting Information Available: Experimental procedures and compound characterization data. This material is available free of charge via the Internet at http://pubs.acs.org.A method for catalytic asymmetric γ sulfenylation of carbonyl compounds has been developed. In the presence of an appropriate catalyst, thiols not only add to the γ position of allenoates, overcoming their propensity to add to the β position in the absence of a catalyst, but do so with very good enantioselectivity. Sulfur nucleophiles are now added to the three families of nucleophiles (carbon, nitrogen, and oxygen) that had earlier been shown to participate in catalyzed γ additions. The phosphine catalyst of choice, TangPhos, had previously only been employed as a chiral ligand for transition metals, not as an efficient enantioselective nucleophilic catalyst.National Institutes of Health (U.S.)National Institute of General Medical Sciences (U.S.) (R01-GM57034)Merck & Co.Novartis (Firm

A Guide to Directing Group Removal: 8‐Aminoquinoline

The use of directing groups allows high levels of selectivity to be achieved in transition metal‐catalyzed transformations. Efficient removal of these auxiliaries after successful functionalization, however, can be very challenging. This review provides a critical overview of strategies used for removal of Daugulis’ 8‐aminoquinoline (2005–2020), one of the most widely used N,N‐bidentate directing groups. The limitations of these strategies are discussed and alternative approaches are suggested for challenging substrates. Our aim is to provide a comprehensive end‐users’ guide for chemists in academia and industry who want to harness the synthetic power of directing groups—and be able to remove them from their final products

What about the partner? -factors associated with patient-perceived partner dyspareunia in men with Peyronie\u27s disease

Background: Limited data are available on how partners of men with Peyronie\u27s disease (PD) are affected by the disease. We sought to characterize PD patients whose curvatures result in pain for their partners during penetrative intercourse. Methods: We queried a database of all men undergoing initial evaluation for PD at a single clinic between March 2014 and June 2016. Patients were administered a questionnaire regarding sexual health concerns with domains including erectile dysfunction, ejaculatory dysfunction, libido, and penile curvature. In the penile curvature section, patients were specifically asked: Does the curvature cause your partner any pain during penetrative intercourse? (Y/N). Patients\u27 partners were not directly evaluated for conditions associated with dyspareunia. Additionally, patients interested in treatment for PD underwent objective curve assessment after intracavernosal injection of erectogenic medications along with penile duplex Doppler ultrasound. Statistical analysis was performed to identify differences in clinicopathologic variables and patient-responses to questionnaire prompts between patients who did and did not report partner pain with intercourse. Results: A total of 322 patients with information available on partner pain were included in the study. Patients who reported partner pain had significantly higher subjective erectile rigidity (mean 5.9/10 Conclusions: Men with superior erectile function, higher degrees of penile curvature and ventral curvatures were more likely to report partner pain during penetrative intercourse. These specific disease characteristics reported in this series may assist clinicians in identifying men who are more motivated to select more invasive therapies

Coherent states for polynomial su(1,1) algebra and a conditionally solvable system

In a previous paper [{\it J. Phys. A: Math. Theor.} {\bf 40} (2007) 11105], we constructed a class of coherent states for a polynomially deformed $su(2)$ algebra. In this paper, we first prepare the discrete representations of the nonlinearly deformed $su(1,1)$ algebra. Then we extend the previous procedure to construct a discrete class of coherent states for a polynomial su(1,1) algebra which contains the Barut-Girardello set and the Perelomov set of the SU(1,1) coherent states as special cases. We also construct coherent states for the cubic algebra related to the conditionally solvable radial oscillator problem.Comment: 2 figure

Commissioning of the vacuum system of the KATRIN Main Spectrometer

The KATRIN experiment will probe the neutrino mass by measuring the beta-electron energy spectrum near the endpoint of tritium beta-decay. An integral energy analysis will be performed by an electro-static spectrometer (Main Spectrometer), an ultra-high vacuum vessel with a length of 23.2 m, a volume of 1240 m^3, and a complex inner electrode system with about 120000 individual parts. The strong magnetic field that guides the beta-electrons is provided by super-conducting solenoids at both ends of the spectrometer. Its influence on turbo-molecular pumps and vacuum gauges had to be considered. A system consisting of 6 turbo-molecular pumps and 3 km of non-evaporable getter strips has been deployed and was tested during the commissioning of the spectrometer. In this paper the configuration, the commissioning with bake-out at 300{\deg}C, and the performance of this system are presented in detail. The vacuum system has to maintain a pressure in the 10^{-11} mbar range. It is demonstrated that the performance of the system is already close to these stringent functional requirements for the KATRIN experiment, which will start at the end of 2016.Comment: submitted for publication in JINST, 39 pages, 15 figure

Diastereo- and Enantioselective Pd(II)-Catalyzed Additions of 2-Alkylazaarenes to N-Boc Imines and Nitroalkenes

A chiral Pd(II)–bis(oxazoline) complex was found to be highly effective in promoting the first direct diastereo- and enantioselective addition of alkylazaarenes to N-Boc aldimines and nitroalkenes under mild conditions. Deprotection of Boc-protected products proceeded readily to provide amines in high yields

Cardiorespiratory fitness is associated with hard and light intensity physical activity but not time spent sedentary in 10–14 year old schoolchildren: the HAPPY study

Sedentary behaviour is a major risk factor for developing chronic diseases and is associated with low cardiorespiratory fitness in adults. It remains unclear how sedentary behaviour and different physical activity subcomponents are related to cardiorespiratory fitness in children. The purpose of this study was to assess how sedentary behaviour and different physical activity subcomponents are associated with 10–14 year-old schoolchildren's cardiorespiratory fitness

Investigating optimal accelerometer placement for energy expenditure prediction in children using a machine learning approach

Accurate measurement of energy expenditure (EE) is imperative for identifying and targeting health-associated implications. Whilst numerous accelerometer-based regression equations to predict EE have been developed, there remains little consensus regarding optimal accelerometer placement. Therefore, the purpose of the present study was to validate and compare artificial neural networks (ANNs) developed from accelerometers worn on various anatomical positions, and combinations thereof, to predict EE.Twenty-seven children (15 boys; 10.8  ±  1.1 years) participated in an incremental treadmill test and 30 min exergaming session wearing a portable gas analyser and nine ActiGraph GT3X+  accelerometers (chest and left and right wrists, hips, knees, and ankles). Age and sex-specific resting EE equations (Schofield) were used to estimate METs from the oxygen uptake measures. Using all the data from both exergames, incremental treadmill test and the transition period in between, ANNs were created and tested separately for each accelerometer and for combinations of two or more using a leave-one-out approach to predict EE compared to measured EE. Six features (mean and variance of the three accelerometer axes) were extracted within each 15 s window as inputs in the ANN. Correlations and root mean square error (RMSE) were calculated to evaluate prediction accuracy of each ANN, and repeated measures ANOVA was used to statistically compare accuracy of the ANNs.All single-accelerometer ANNs and combinations of two-, three-, and four-accelerometers performed equally (r  =  0.77–0.82), demonstrating higher correlations than the 9-accelerometer ANN (r  =  0.69) or the Freedson linear regression equation (r  =  0.75). RMSE did not differ between single-accelerometer ANNs or combinations of two, three, or four accelerometers (1.21–1.31 METs), demonstrating lower RMSEs than the 9-accelerometer ANN (1.46 METs) or Freedson equation (1.74 METs).These findings provide preliminary evidence that ANNs developed from single accelerometers mounted on various anatomical positions demonstrate equivalency in the accuracy to predict EE in a semi-structured setting, supporting the use of ANNs in improving EE prediction accuracy compared with linear regression