Diastereoselective Synthesis of Planar Chiral N-Substituted Ferrocenes Derived from Epimeric Imidazolones and their Application to Asymmetric Hydrogenation of Quinolines

This thesis describes the synthesis and use of an N-substituted ferrocene bearing a proline-derived chiral directing group and diastereoselective lithiation-electrophile quench of the pro-Sp hydrogen of the ferrocene to give planar chiral products in >95:5 dr. The auxiliary group is found to be stable to lithium bases of types RLi and R2NLi giving the same diastereoselectivity. The anti- epimer of the previously mentioned syn auxiliary induces lithiation of pro Rp rather than pro Sp hydrogen in >95:5 dr. Upon electrophile quench and elimination, the enantiomer of the syn-derived planar chiral imidazolone is obtained. Hence, this method provides a practical way to prepare planar chiral enantiomers in this series without the use of a more expensive D-proline derived starting material. The syn and anti epimers have β, γ-stereogenic centers and the origin of stereoselectivity in lithiation appears to be driven by the conformational bias exerted by the β-silyloxy moiety in each chiral auxiliary. In the thesis, this conclusion is supported using insensitivity of lithiation selectivity to the bulkiness of the base, comparison of enantiomers, deuteration experiments, nOe difference studies and computational modeling of the ground states and lithiation transition states for both substrates. The products are then converted to ligand precursors to make iridium and rhodium complexes. Among them, one of the cationic iridium complex is found to be effective in the asymmetric hydrogenation of 2-substituted quinolines with enantioselectivities up to 80% at pressures as low as 5 atm.

The Pelican - Official Line-Up of All Women's International Air Race

A listing of the pilots competing in the All Women's International Air Race, 1953.

Photograph - Percy Band Eating Watermelon Close-up

Black and white photo of Percy Band eating watermelon. This picture is 5 cm x 4 cm.

Parent Prediction of Autism Spectrum Disorder in Infants At Risk: A Follow-up Study

Later-born siblings of children with autism spectrum disorder (ASD) are considered at biological risk for ASD and the broader autism phenotype. Early screening may detect early signs of ASD and facilitate intervention as soon as possible. This follow-up study revisits and re-examines a second-degree autism screener for children at biological risk of autism, the Parent Observation Early Markers Scale (POEMS, Feldman et al., 2012). Using available follow-up information, 110 children (the original 108 infants plus 2 infants recruited after the completion of the original study) were divided into three groups: diagnosed group (n = 13), lost diagnosis group (n = 5), and undiagnosed group (n = 92). The POEMS continued to show acceptable predictive validity. The POEMS total scores and mean number of elevated items were significantly higher in the diagnosed group than the undiagnosed group. The lost diagnosis group did not differ from the undiagnosed group on POEMS total scores and elevated items at any age, but the lost diagnosis group had significantly lower total scores and number of elevated items than the diagnosed group starting at 18 months. Both ASD core and subsidiary behaviours differentiated the diagnosed and undiagnosed groups from 9−36 months of age. Using 70 as a cut-off score, sensitivity, specificity, and positive predictive value (PPV) were .69, .84, and .38, respectively. The study provides further evidence that the POEMS may serve as a low-cost early screener for ASD in at risk children and pinpoint specific developmental and behavioural problems that may be amenable to very early intervention.

Letter to S.D. Woodruff stating that Mr. Mater wishes to take up his mortgage signed Jarvis, Conklin and Co

Letter (1 page, typed) to S.D. Woodruff stating that Mr. Mater wishes to take up his mortgage. It is signed Jarvis, Conklin and Co., Aug. 18, 1884.

Blocking Top-down awareness of Kanizsa Figures: An ERP Investigation into Bottom-up Processing of Illusory Contours

Neural models of the processing of illusory contour (ICs) diverge from one another in terms of their emphasis on bottom-up versus top-down constituents. The current study uses a dichoptic fusion paradigm to block top-down awareness of ICs in order to examine possible bottom-up effects. Group results indicate that the N170 ERP component is particularly sensitive to ICs at central occipital sites when top-down awareness of the stimulus is permitted. Furthermore, single-subject statistics reveal that the IC N170 ERP effect is highly variable across individuals in terms of timing and topographical spread. The results suggest that the ubiquitous N170 effect to ICs found in the literature depends, at least in part, on participants’ awareness of the stimulus. Therefore a strong bottom-up model of IC processing at the time of the N170 is unlikely.

Voucher from the Engineer Department of Port Dalhousie and Thorold Railway Extension for W.G. Thompson for the Northern Division. There are attached notes from the Welland Railway Company to John Mitchell for putting up shelves; to William Waud, staff; and to William Martin to repair the office (copy), June 10, 1857

Voucher from the Engineer Department of Port Dalhousie and Thorold Railway Extension for W.G. Thompson for the Northern Division. There are attached notes from the Welland Railway Company to John Mitchell for putting up shelves; to William Waud, staff; and to William Martin to repair the office (copy), June 10, 1857.

Voucher #22 to James McCoppen (copy) which includes a letter from James McCoppen regarding a claim for having water backed up into his grain and grass by the embankment of the railroad. The letter is dated June 24, 1857 and the voucher is dated Jul. 1, 1857

Voucher #22 to James McCoppen (copy) which includes a letter from James McCoppen regarding a claim for having water backed up into his grain and grass by the embankment of the railroad. The letter is dated June 24, 1857 and the voucher is dated Jul. 1, 1857.

Letter to S.D. Woodruff from George H. Gillespie regarding setting up a meeting of the members of the Long Point Company

Letter to S.D. Woodruff from George H. Gillespie regarding setting up a meeting of the members of the Long Point Company, Dec. 21, 1866.

Letter to S.D. Woodruff from John I. Mackenzie saying that he is closing up the commissariat accounts at Long Point

Letter to S.D. Woodruff from John I. Mackenzie saying that he is closing up the commissariat accounts at Long Point. There is still an amount outstanding and he asks Mr. Woodruff to send a cheque. He hopes that Mr. Woodruff had a good time at Long Point (2 pages, handwritten), Nov. 23, 1881.

Totals of free goods up – class 3 and class 4

Totals of free goods up – class 3 and class 4 (1 page, handwritten), n.d.

7-Up Radio ad with Eartha Kitt

A one minute radio advertising for the soft drink 7-Up featuring the voice of Eartha Kitt.

Etude théorique des propriétés électroniques et optiques des super-réseaux de Si/SiO2

FRANCAIS: L'observation d'une intense luminescence dans les super-réseaux de Si/SiO2 a ouvert de nouvelles avenues en recherche théorique des matériaux à base de silicium, pour des applications éventuelles en optoélectronique. Le silicium dans sa phase cristalline possède un gap indirect, le rendant ainsi moins intéressant vis-à-vis d'autres matériaux luminescents. Concevoir des matériaux luminescents à base de silicium ouvrira donc la voie sur de multiples applications. Ce travail fait état de trois contributions au domaine. Premièrement, différents modèles de super-réseaux de Si/SiO2 ont été conçus et étudiés à l'aide de calculs ab initio afin d'en évaluer les propriétés structurales, électroniques et optiques. Les deux premiers modèles dérivés des structures cristallines du silicium et du dioxyde de silicium ont permis de démontrer l'importance du rôle de l'interface Si/SiO2 sur les propriétés optiques. De nouveaux modèles structurellement relaxés ont alors été construits afin de mieux caractériser les interfaces et ainsi mieux évaluer la portée du confinement sur les propriétés optiques. Deuxièmement, un gap direct dans les modèles structurellement relaxés a été obtenu. Le calcul de l'absorption (par l'application de la règle d'or de Fermi) a permis de confirmer que les propriétés d'absorption (et d'émission) du silicium cristallin sont améliorées lorsque celui-ci est confiné par le SiO2. Un décalage vers le bleu avec accroissement du confinement a aussi été observé. Une étude détaillée du rôle des atomes sous-oxydés aux interfaces a de plus été menée. Ces atomes ont le double effet d'accroître légèrement le gap d'énergie et d'aplanir la structure électronique près du niveau de Fermi. Troisièmement, une application directe de la théorique des transitions de Slater, une approche issue de la théorie de la fonctionnelle de la densité pour des ensembles, a été déterminée pour le silicium cristallin puis comparée aux mesures d'absorption par rayons X. Une très bonne correspondance entre cette théorie et l'expérience est observée. Ces calculs ont été appliqués aux super-réseaux afin d'estimer et caractériser leurs propriétés électroniques dans la zone de confinement, dans les bandes de conduction.

How to measure the intensity of competition : the mark-up estates for turkish manufacturing industries.

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Speak english, little chats a help to learn conversational english,drawn up after the new method of teaching

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