289 research outputs found

    A π-Extended Donor-Acceptor-Donor Triphenylene Twin linked via a Pyrazine-bridge

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    Beta-amino triphenylenes can be accessed via palladium catalyzed amination of the corresponding triflate using benzophe-none imine. Transformation of amine 6 to benzoyl amide 18 is also straightforward and its wide mesophase range demon-strates that the new linkage supports columnar liquid crystal formation. Amine 6 also undergoes clean aerobic oxidation to give a new twinned structure linked through an electron-poor pyrazine ring. The new discotic liquid crystal motif contains donor and acceptor fragments, and is more oval in shape rather than disk-like. It forms a wide range columnar mesophase. Absorption spectra are strong and broad; emission is also broad and occurs with a Stokes shift of ca. 0.7 eV, indicative of charge-transfer characte

    Copper-catalysed selective hydroamination reactions of alkynes

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    The development of selective reactions that utilize easily available and abundant precursors for the efficient synthesis of amines is a long-standing goal of chemical research. Despite the centrality of amines in a number of important research areas, including medicinal chemistry, total synthesis and materials science, a general, selective and step-efficient synthesis of amines is still needed. Here, we describe a set of mild catalytic conditions utilizing a single copper-based catalyst that enables the direct preparation of three distinct and important amine classes (enamines, α-chiral branched alkylamines and linear alkylamines) from readily available alkyne starting materials with high levels of chemo-, regio- and stereoselectivity. This methodology was applied to the asymmetric synthesis of ​rivastigmine and the formal synthesis of several other pharmaceutical agents, including ​duloxetine, ​atomoxetine, ​fluoxetine and ​tolterodine.National Institutes of Health (U.S.) (GM58160

    Medical student attitudes toward video games and related new media technologies in medical education

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    <p>Abstract</p> <p>Background</p> <p>Studies in K-12 and college students show that their learning preferences have been strongly shaped by new media technologies like video games, virtual reality environments, the Internet, and social networks. However, there is no known research on medical students' game experiences or attitudes towards new media technologies in medical education. This investigation seeks to elucidate medical student experiences and attitudes, to see whether they warrant the development of new media teaching methods in medicine.</p> <p>Methods</p> <p>Medical students from two American universities participated. An anonymous, 30-item, cross-sectional survey addressed demographics, game play experience and attitudes on using new media technologies in medical education. Statistical analysis identified: 1) demographic characteristics; 2) differences between the two universities; 3) how video game play differs across gender, age, degree program and familiarity with computers; and 4) characteristics of students who play most frequently.</p> <p>Results</p> <p>217 medical students participated. About half were female (53%). Respondents liked the idea of using technology to enhance healthcare education (98%), felt that education should make better use of new media technologies (96%), and believed that video games can have educational value (80%). A majority (77%) would use a multiplayer online healthcare simulation on their own time, provided that it helped them to accomplish an important goal. Men and women agreed that they were most inclined to use multiplayer simulations if they were fun (97%), and if they helped to develop skill in patient interactions (90%). However, there was significant gender dissonance over types of favorite games, the educational value of video games, and the desire to participate in games that realistically replicated the experience of clinical practice.</p> <p>Conclusions</p> <p>Overall, medical student respondents, including many who do not play video games, held highly favorable views about the use of video games and related new media technology in medical education. Significant gender differences in game play experience and attitudes may represent male video game design bias that stresses male cognitive aptitudes; medical educators hoping to create serious games that will appeal to both men and women must avoid this.</p

    Unexpectedly high barriers to M–P rotation in tertiary phobane complexes : PhobPR behavior that is commensurate with tBu2PR

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    The four isomers of 9-butylphosphabicyclo[3.3.1]nonane, s-PhobPBu, where Bu = n-butyl, sec-butyl, isobutyl, tert-butyl, have been prepared. Seven isomers of 9-butylphosphabicyclo[4.2.1]nonane (a5-PhobPBu, where Bu = n-butyl, sec-butyl, isobutyl, tert-butyl; a7-PhobPBu, where Bu = n-butyl, isobutyl, tert-butyl) have been identified in solution; isomerically pure a5-PhobPBu and a7-PhobPBu, where Bu = n-butyl, isobutyl, have been isolated. The σ-donor properties of the PhobPBu ligands have been compared using the JPSe values for the PhobP(═Se)Bu derivatives. The following complexes have been prepared: trans-[PtCl2(s-PhobPR)2] (R = nBu (1a), iBu (1b), sBu (1c), tBu (1d)); trans-[PtCl2(a5-PhobPR)2] (R = nBu (2a), iBu (2b)); trans-[PtCl2(a7-PhobPR)2] (R = nBu (3a), iBu (3b)); trans-[PdCl2(s-PhobPR)2] (R = nBu (4a), iBu (4b)); trans-[PdCl2(a5-PhobPR)2] (R = nBu (5a), iBu (5b)); trans-[PdCl2(a7-PhobPR)2] (R = nBu (6a), iBu (6b)). The crystal structures of 1a–4a and 1b–6b have been determined, and of the ten structures, eight show an anti conformation with respect to the position of the ligand R groups and two show a syn conformation. Solution variable-temperature 31P NMR studies reveal that all of the Pt and Pd complexes are fluxional on the NMR time scale. In each case, two species are present (assigned to be the syn and anti conformers) which interconvert with kinetic barriers in the range 9 to >19 kcal mol–1. The observed trend is that, the greater the bulk, the higher the barrier. The magnitudes of the barriers to M–P bond rotation for the PhobPR complexes are of the same order as those previously reported for tBu2PR complexes. Rotational profiles have been calculated for the model anionic complexes [PhobPR-PdCl3]− using DFT, and these faithfully reproduce the trends seen in the NMR studies of trans-[MCl2(PhobPR)2]. Rotational profiles have also been calculated for [tBu2PR-PdCl3]−, and these show that the greater the bulk of the R group, the lower the rotational barrier: i.e., the opposite of the trend for [PhobPR-PdCl3]−. Calculated structures for the species at the maxima and minima in the M–P rotation energy curves indicate the origin of the restricted rotation. In the case of the PhobPR complexes, it is the rigidity of the bicycle that enforces unfavorable H···Cl clashes involving the Pd–Cl groups with H atoms on the α- or β-carbon in the R substituent and H atoms in 1,3-axial sites within the phosphabicycle