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Thesis advisor: Jeffrey A. Byers / Chapter 1: There are a limited number of examples of metal-catalyzed Brook rearrangements in the literature, none of which involve ruthenium, rhodium, or iridium which are common ketone hydrogenation catalysts. The content of this chapter introduces the traditional Brook rearrangement and its advantages and disadvantages in chemical synthesis. Furthermore, the few examples of metal-catalyzed Brook rearrangements of acylsilanes and structurally similar moieties are discussed. Chapter 2: Utilizing a Brook rearrangement under hydrogenation or transfer hydrogenation conditions opens up a new area of catalytic reactivity that has not been fully explored. To our knowledge, metal complexes based on ruthenium and rhodium have never been shown to catalyze a Brook rearrangement of acylsilanes. This chapter describes the mechanistic implications of a Brook rearrangement under hydrogenation or transfer hydrogenation conditions as well as the first example of a ruthenium-catalyzed Brook rearrangement of aryl acylsilanes. Chapter 3: Pioneering work performed by Jeffrey Johnson and co-workers in the area of catalytic coupling of acylsilanes and various electrophiles showed that formation of new C-C bonds through a Brook rearrangement can be a powerful synthetic tool. In this chapter, we investigate an intermolecular coupling of aryl acylsilanes and aldehydes through a metal-catalyzed Brook rearrangement under transfer hydrogenation conditions to yield two synthetically useful motifs, specifically oxygenated bicyclic compounds. A reaction screen was performed on the coupling capabilities of these two species with various ruthenium and rhodium catalysts. The result of the screen was synthesis of a silyl ether acetal through employing the starting material as the reducing equivalent. Additionally, mechanistic insight was gained to further develop the proposed methodology. Chapter 4: An intramolecular approach to achieving coupling of acylsilanes and many different types of electrophiles was envisioned as a way of furnishing synthetically useful bicyclic compounds in one step. The focus of this chapter is the synthesis of a novel acylsilane that we proposed could undergo an intramolecular cross coupling reaction under transfer hydrogenation conditions. The conclusion of this chapter outlines the future direction of the project, which entails a new route to an intermolecular cross coupling of acylsilanes and various electrophiles. Published work from Michael Krische's laboratory helped us envision a different type of acylsilane, specifically an α,β-unsaturated acylsilane, in which binding to a metal center would proceed through a π-allyl intermediate. Ongoing efforts in the coupling of α,β-unsaturated acylsilanes with electrophiles are currently underway. / Thesis (MS) — Boston College, 2013. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: James P. Morken / Detailed within this dissertation are three new reactions involving allylboron reagents. Chapter 1 describes the development of Pd-catalyzed allyl-allyl cross-coupling for the preparation of enantioenriched all-carbon quaternary stereogenic centers. This methodology represents a novel approach to a significant challenge for synthetic chemists. Subsequently, an allyl-allyl cross-coupling is described which generates functionally differentiated 1,5-dienes. Such structures allow for several chemoselective manipulations, which add a significant practical note to this cross-coupling methodology. Chapter 2 details the development of the allylboration of nitrosobenzene with (Z)-crotylboronate derivatives, which results in the formation of branched allylic alcohols. This methodology provides a regioselective complement to standard boron oxidation conditions. / Thesis (PhD) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: James P. Morken / Described herein are three distinct projects centered on the formation and use of carbon-boron bonds. In the first, the enantioselective platinum-catalyzed 1,4-diboration of trans-1,3-dienes is advanced in both selectivity and scope through the development of a novel class of electron rich chiral monodentate phosphines. Under the action of the new ligands, highly selective diboration is maintained at reduced loadings of catalyst. Secondly, enantioenriched 1,2-bis(pinacol boronates) are engaged in regioselective Suzuki-Miyaura cross-coupling with aryl and vinyl electrophiles. A tandem diboration cross-coupling sequence is successfully implemented to afford homobenzylic and homoallylic pinacol boronates directly from terminal olefins, which subsequently undergo oxidation, amination or homologation of the remaining carbon-boron bond to arrive at a range of enantioenriched products. Lastly, aryl electrophiles containing tethered allylboronate units undergo efficient intramolecular coupling in the presence of a chiral palladium catalyst to give enantioenriched carbocyclic products. / Thesis (PhD) — Boston College, 2014. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

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Notre étude concerne la précarité, la violence et le danger chez les adolescents du quartier Hatikva, situé dans la banlieue-sud de Tel Aviv en Israël ; et la prise en charge de ces adolescents par l'institution Beit Ham au moyen de la psychothérapie institutionnelle. La précarité organise ici le quotidien de l'adolescent, ce déjà enfant : ici, l'enfant et l'adolescent sont confrontés à la précarité dans les domaines les plus élémentaires soit l'alimentaire, le jeu, le développement, l'accueil familial et sociétal, la protection, l'espace et la relation. C'est alors ce rapport intersignifiant élémentaire, structurant, entre ensemble et partie, entre nécessité et légitimité qui manque ou est très insuffisant pour permettre à la parole et à la demande de l'adolescent de s'articuler à l'extérieur, et par conséquent de constituer un appui et un recours. D'où notre problématique : la violence et le danger chez l'adolescent sont fonction de la précarité de la relation. Alors c'est cette "relation de connexion" (J. Lacan) élémentaire, ce rapport intersignifiant structurant entre énoncé et énonciation, entre "matériel signifiant" (J. Lacan) et sens, entre organisation déjà là et une présence qui n'opère pas. Ce qui confronte nombre d'adolescents et d'enfants à une difficulté de rencontre entre l'espace psychique et l'espace social, à une errance psychique et sociale, et à une difficulté de s'appuyer et de recourir au soutien extérieur pour faire face aux violences et aux dangers fortement présents dans leur milieu de vie. Mais ici c'est cet "espace du politique" (H. Arendt), cet espace de la relation, cette "signification de la participation" (L. Lavelle) qui sont sérieusement à interroger; soit ce "pas décisif culturel" (S. Freud). Mais la situation est critique car le potentiel de danger est très grand pour beaucoup de ces enfants et de ces adolescents. C'est donc la politique que ces adolescents interpellent directement, et nous avec : soit le sérieux de cette garantie d'un espace commun pour tous, du droit à la Cité, du droit à l'accueil et à la protection ; soit ces fondamentaux politiques non négociables pour la présence d'un enfant et d'un adolescent au monde c'est-à-dire de cet espace de la relation, de cet espace du rapport – intersignifiant – élémentaire et structurant. Qu'en est-il de cette existence politique d'un adolescent et d'un enfant, dont l'inconscient semble l'expression, quand le préjudice politique, quand la « misère symbolique » (P.-L. Assoun) auxquels sont confrontés tant d'enfants et d'adolescents sur ce terrain, ne permettent plus cette solidarité – existentielle – entre une présence au monde et espace, relation et structure, ou encore ce rapport intersignifiant élémentaire entre présence et participation, entre unité et continuité? / Our study concerns the precariousness, danger and violence among adolescents in the Hatikva neighborhood, situated in the southern suburbs of Tel Aviv in Israel; and the care provided for these adolescents by the Beit Ham institution by means of institutional psychotherapy. Here, precariousness rules over the daily life of the adolescent, who is yet a child: here, the child and the adolescent are confronted with precariousness in the most basic of domains, be it that of nutrition, play, development, family and societal climate, protection, space, and relationships. It is thus this relation of basic, structuring, cross-signifying relation, between whole and part, between necessity and legitimacy, which Is lacking or which is too insufficient to allow the verbal exteriorization of the adolescent’s own speech and demands, and thereby constitute support and remedy. Hence, our difficulty: violence and danger among adolescents are linked to the precariousness of the relationships. So it is this basic ”relationship of connection” (J. Lacan), this structuring cross-signifying relation between an utterance and the act of uttering itself, between “signifying material” (J. Lacan) and sense, between the existing organisation and a non-operating presence. Which makes it that numerous adolescents and children are confronted with a matching difficulty between physical and social space, with a psychic and social vagrancy, and with a difficulty to draw on and to resort to external support in order to face the ever-present violence and danger in their living environment. But in this case, it is this “political space” (H. Arendt), this relational space, this “significance of participation” (L. Lavelle) that are to be seriously questioned; or this “decisive cultural step” (S. Freud). But the situation is a critical one because the potential danger is very high for many of these children and adolescents. It is thus politics that these adolescents are directly calling out to, along with us: either the reliability of this guarantee of a common space for all, the right to a housing project, the right to acceptance and protection; or these fundamental, non-negotiable politics for the presence of a child or an adolescent in the world, that is to say, in this relational space, this connective space – cross-signifying – basic and structuring. What about this political existence of an adolescent and a child, whose unawareness is taken as expression, when the political prejudice, the “symbolic misery” (P.-L. Assoun) that so many children are confronted with in this region, no longer allow for this existential solidarity between a presence in the world and in the physical space, relationship and structure, or even this basic cross-signifying relation between presence and participation, between unity and continuity?

To gain an understanding of children’s social milieu, this study explored international children’s phenomenology about their social networks, stressors, and supports using the ecomap, a graphic tool that maps children’s social relationships and their appraisals of them. Specifically, it addressed the following two research questions using archival ecomap data collected from 816 school-aged children (ages four – 19 years) from 14 cities in 12 countries (Brazil – Manaus, Estonia – Tallinn, Greece – Athens, India – Mumbai, Italy – Padua, Mexico – Xalapa, Romania – Bucharest, Russia – Samara, Slovak Republic – Košice, Sri Lanka – Negombo, Tanzania – Arusha, and the United States – Boston, Massachusetts; Mayagüez, Puerto Rico; New Orleans, Louisiana): (a) What are the characteristics of international children’s social networks, and what cross-cultural patterns exist; and (b) Who and what do children consider their social supports and social stressors, and what cross-cultural patterns emerge? The nature of the ecomap drawings and their associated narratives allowed for a concurrent mixed methods approach to be used to identify cross-cultural phenomenological patterns about the structures (network size, embeddedness, and network composition), functions (stressor and support types), and evaluations (relationship appraisals) of children’s social worlds. Considerable diversity was found in the data, but a number of notable cross-site, cross-gender, and cross-age patterns were identified. In general, children in this sample reported a trimmed mean network size of 7.87 (SD = 3.61), with middle school students reporting the largest (M = 8.78). Embeddedness, measured as the balance of perceived stress and supports (Nastasi & Borja, 2015; Summerville, 2013), also was generally positive, suggesting that children generally perceive themselves to be connected to their social networks. Most commonly reported members included home parent/caregivers, friends/peers, extended family members, and siblings; and across grade levels, sites, and gender, network members were generally appraised positively. When asked about the ways that network members support or trigger distress, youth in this sample described over 50 stress and support themes, most of which related to interpersonal relationships and interactions. The results of the current study not only contributes to the literature on children’s stressors and supports, but also build on Nastasi and colleagues’ Promoting Psychological Well-Being Globally project (PPWBG; Nastasi & Borja, 2015), whose international team collected the ecomap data to understand children’s well-being and the culturally- and developmentally-unique factors that influence them. / 1 / Amanda P Borja

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The effects of expertise, such as better recognition of own-race than other-race faces, have been attributed either to poor encoding of configural information (the dual-mode theory) or to representation of faces on dimensions attuned to own-race faces and, hence, inappropriate for coding of other-race faces (the ABC model). Neither framework alone has been able to account for the variety of past results. It is proposed that a composite account derived from the dual-mode theory and the ABC model may offer a more complete explanation of the effects of race. To evaluate the composite account, six experiments using perceptual paradigms were carried out. The structure of face space and the effects of expertise on configural processing were assessed in a dissimilarity perception task (Experiment 1). Caucasian and Chinese participants judged dissimilarity of own-race and other-race faces with various configural distortions relative to their unaltered versions. As predicted by the composite account, face spaces derived from the dissimilarity ratings for own-race and other-race faces were comparable. Consistent with the premise that expertise affects configural coding, Caucasian participants exhibited greater sensitivity to configural changes of own-race than other-race faces. The effects of expertise on configural encoding were further examined in a bizarreness perception paradigm (Experiments 2-4). Caucasian participants rated bizarreness of unaltered and distorted faces rotated from upright to inverted in 15� increments. The distortions involved either simple component alterations (i.e., whitened pupils and blackened teeth), global configural changes (i.e., inverted eyes and mouth), or more local configural transformations (e.g., moving the eyes closer together and upwards, and shifting the mouth down). Similar bizarreness ratings for all faces with component distortions confirmed that expertise does not affect processing of simple component information. Differences in the perceived bizarreness of own-race and other-race faces in the unaltered and global configural distortion conditions corroborated the hypothesis that expertise influences holistic configural encoding. Variations in the perceived bizarreness of faces with more local configural changes, however, indicated that expertise might also affect local configural coding. The effects of expertise on local configural processing were further examined in a discrimination paradigm (Experiments 5 and 6). Participants made same-different decisions with upright and inverted face pairs comprising either two identical faces (same trials) or unaltered and distorted versions of the same face (different trials). To distinguish between holistic and local processing of configural information, partial faces were created in addition to whole faces. Higher accuracy for own-race than other-race faces at both upright and inverted orientations in both whole and partial face conditions substantiated the argument that expertise modulates local configural encoding. Altogether, the present investigation offers direct evidence for the composite account of the effects of race. As ventured by the composite account, the own-race face bias in face perception was shown to be due to variations in configural processing. In addition, the reported experiments support the argument that configural information can be encoded both locally and holistically.

With minority Americans expected to comprise more than 40% of the U.S population by 2035 and 47% by 2050 and substance abuse epidemic with 23.5 million nationwide in need for treatment, there is a growing need for cross-cultural counseling competence among substance abuse counselors. This study examined substance abuse counselors' level of cross-cultural counseling competence in the Commonwealth of Pennsylvania. The research method used was quantitative in nature. Substance abuse counselors were asked to self-assess their level of competence by completing a questionnaire and modified Cross-Cultural Counseling Inventory Revised (CCCI-R) subscales to determine whether counselor's gender, level of education, field of study, ethnicity, and number of continuing education make a difference in level of cultural competence. CCCI-R was proven to have acceptable content validity and is representative of domain of cross-cultural counseling competence. A total of 109 participants completed the questionnaire and CCCI-R. <br>The result of a one-way ANOVA in the mean scores revealed no significant difference between counselor's gender, level of education, field of study, ethnicity, and cultural competence. The post hoc data analysis in the field of study indicated those counselors who were trained in Counseling and Social Work scored higher than counselors trained in Psychology. The results of the Pearson Correlation revealed no relationship between the number of continuing education hours and substance abuse counselor's level of cross-cultural counseling competence. After the testing of hypotheses of this study, the results indicated no significant differences in the mean scores of the independent variables and substance abuse counselor's level of cross-cultural competence. / School of Education / Counselor Education and Supervision (ExCES) / PhD / Dissertation