1,179 research outputs found

    The Evaluation of Novel Camphor-derived Ligands as Catalysts in the Asymmetric Henry Reaction

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    The evaluation of a series of camphor-derived ligands as catalysts in the asymmetric Henry reaction is reported. The synthesis of two novel derivatives is detailed and these molecules are also screened as catalysts in this reaction. The single crystal X-ray structure of one of the novel compounds is reported. The reaction is catalyzed with moderate to excellent yields and moderate enantioselectivity.Keywords: Camphor, asymmetric catalysis, Henry reaction, chiral ligand

    Synthesis of Novel 3-Hydroxy-3-pyridylcamphor Derivatives

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    The synthesis of a series of five novel precursor compounds derived from (R)-(+)-camphor is reported. From these precursors, a further four novel pyridyl alcohol ligands were synthesized. The molecules represent the first reported examples where the pyridyl and hydroxyl moieties are pendant on the C3 position of the camphor skeleton. The regioselective synthesis was investigated and an efficient method was identified. The final ligands were obtained in moderate yield with absolute regio- and stereoselective control. The molecules were screened as catalysts in the alkylation of aldehydes with diethylzinc in order to compare the new arrangement of donor groups with previously reported results obtained with C2 pendant ligands. The results demonstrated a significant improvement for the synthesized C3 pendant ligands over previous C2 examples with moderate yields and up to 85 % ee being obtained.Keywords: Chiral, camphor ligands, pyridyl alcohols, asymmetric alkylation reactionsPDF and Supplementry file attache

    The Evaluation of Novel Camphor-derived Pyridyl Ligands as Catalysts in the Asymmetric Diels-Alder Reaction of Cyclopentadiene with 3-Acryloyl-2-oxazolidinone

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    A series of camphor-derived pyridyl ligands were evaluated in the Diels-Alder reaction of 3-acryloyl-2-oxazolidinone 1 with cyclopentadiene 2. High yields with good endo:exo selectivity, but only moderate enantioselectivities (43 % ee), were obtained. The structures of the copper (II) complexes of the ligands were calculated using ONIOM density functional theory and the results suggest that chiral induction to the alkene functional group is indeed lacking. This explains the moderate experimental selectivities obtained.Keywords: Camphor ligands, asymmetric catalysis, Diels-Alder cycloaddition, computational modellingPDF and Supplementry file attache

    Examining a staging model for anorexia nervosa: empirical exploration of a four stage model of severity.

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    Background: An illness staging model for anorexia nervosa (AN) has received increasing attention, but assessing the merits of this concept is dependent on empirically examining a model in clinical samples. Building on preliminary findings regarding the reliability and validity of the Clinician Administered Staging Instrument for Anorexia Nervosa (CASIAN), the current study explores operationalising CASIAN severity scores into stages and assesses their relationship with other clinical features. Method: In women with DSM-IV-R AN and sub-threshold AN (all met AN criteria using DSM 5), receiver operating curve (ROC) analysis (n = 67) assessed the relationship between the sensitivity and specificity of each stage of the CASIAN. Thereafter chi-square and post-hoc adjusted residual analysis provided a preliminary assessment of the validity of the stages comparing the relationship between stage and treatment intensity and AN sub-types, and explored movement between stages after six months (Time 3) in a larger cohort (n = 171). Results: The CASIAN significantly distinguished between milder stages of illness (Stage 1 and 2) versus more severe stages of illness (Stages 3 and 4), and approached statistical significance in distinguishing each of the four stages from one other. CASIAN Stages were significantly associated with treatment modality and primary diagnosis, and CASIAN Stage at Time 1 was significantly associated with Stage at 6 month follow-up. Conclusions: Provisional support is provided for a staging model in AN. Larger studies with longer follow-up of cases are now needed to replicate and extend these findings and evaluate the overall utility of staging as well as optimal staging models

    Chagas disease: an impediment in achieving the Millennium Development Goals in Latin America

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    <p>Abstract</p> <p>Background</p> <p>Achieving sustainable economic and social growth through advances in health is crucial in Latin America within the framework of the United Nations Millennium Development Goals.</p> <p>Discussion</p> <p>Health-related Millennium Development Goals need to incorporate a multidimensional approach addressing the specific epidemiologic profile for each region of the globe. In this regard, addressing the cycle of destitution and suffering associated with infection with <it>Trypanosoma cruzi</it>, the causal agent of Chagas disease of American trypanosomiasis, will play a key role to enable the most impoverished populations in Latin America the opportunity to achieve their full potential. Most cases of Chagas disease occur among forgotten populations because these diseases persist exclusively in the poorest and the most marginalized communities in Latin America.</p> <p>Summary</p> <p>Addressing the cycle of destitution and suffering associated with <it>T. cruzi </it>infection will contribute to improve the health of the most impoverished populations in Latin America and will ultimately grant them with the opportunity to achieve their full economic potential.</p

    Utilisation of an operative difficulty grading scale for laparoscopic cholecystectomy

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    Background A reliable system for grading operative difficulty of laparoscopic cholecystectomy would standardise description of findings and reporting of outcomes. The aim of this study was to validate a difficulty grading system (Nassar scale), testing its applicability and consistency in two large prospective datasets. Methods Patient and disease-related variables and 30-day outcomes were identified in two prospective cholecystectomy databases: the multi-centre prospective cohort of 8820 patients from the recent CholeS Study and the single-surgeon series containing 4089 patients. Operative data and patient outcomes were correlated with Nassar operative difficultly scale, using Kendall’s tau for dichotomous variables, or Jonckheere–Terpstra tests for continuous variables. A ROC curve analysis was performed, to quantify the predictive accuracy of the scale for each outcome, with continuous outcomes dichotomised, prior to analysis. Results A higher operative difficulty grade was consistently associated with worse outcomes for the patients in both the reference and CholeS cohorts. The median length of stay increased from 0 to 4 days, and the 30-day complication rate from 7.6 to 24.4% as the difficulty grade increased from 1 to 4/5 (both p < 0.001). In the CholeS cohort, a higher difficulty grade was found to be most strongly associated with conversion to open and 30-day mortality (AUROC = 0.903, 0.822, respectively). On multivariable analysis, the Nassar operative difficultly scale was found to be a significant independent predictor of operative duration, conversion to open surgery, 30-day complications and 30-day reintervention (all p < 0.001). Conclusion We have shown that an operative difficulty scale can standardise the description of operative findings by multiple grades of surgeons to facilitate audit, training assessment and research. It provides a tool for reporting operative findings, disease severity and technical difficulty and can be utilised in future research to reliably compare outcomes according to case mix and intra-operative difficulty

    Study of Bc+B_c^+ decays to the K+Kπ+K^+K^-\pi^+ final state and evidence for the decay Bc+χc0π+B_c^+\to\chi_{c0}\pi^+

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    A study of Bc+K+Kπ+B_c^+\to K^+K^-\pi^+ decays is performed for the first time using data corresponding to an integrated luminosity of 3.0 fb1\mathrm{fb}^{-1} collected by the LHCb experiment in pppp collisions at centre-of-mass energies of 77 and 88 TeV. Evidence for the decay Bc+χc0(K+K)π+B_c^+\to\chi_{c0}(\to K^+K^-)\pi^+ is reported with a significance of 4.0 standard deviations, resulting in the measurement of σ(Bc+)σ(B+)×B(Bc+χc0π+)\frac{\sigma(B_c^+)}{\sigma(B^+)}\times\mathcal{B}(B_c^+\to\chi_{c0}\pi^+) to be (9.83.0+3.4(stat)±0.8(syst))×106(9.8^{+3.4}_{-3.0}(\mathrm{stat})\pm 0.8(\mathrm{syst}))\times 10^{-6}. Here B\mathcal{B} denotes a branching fraction while σ(Bc+)\sigma(B_c^+) and σ(B+)\sigma(B^+) are the production cross-sections for Bc+B_c^+ and B+B^+ mesons. An indication of bˉc\bar b c weak annihilation is found for the region m(Kπ+)<1.834GeV ⁣/c2m(K^-\pi^+)<1.834\mathrm{\,Ge\kern -0.1em V\!/}c^2, with a significance of 2.4 standard deviations.Comment: All figures and tables, along with any supplementary material and additional information, are available at https://lhcbproject.web.cern.ch/lhcbproject/Publications/LHCbProjectPublic/LHCb-PAPER-2016-022.html, link to supplemental material inserted in the reference
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