Modifications to the Suzuki reaction and mechanistic insights on the NBS mediated cleavage of benzylidene acetals /

One of the most challenging tasks for a synthetic organic chemist today, is the development of chemo, regio, and stereoselective methodologies toward the total synthesis of macromolecules. r . The objective of my thesis was to develop methodologies towards this end. The first part of my project was to develop highly functionalized chirons from D-glucose, a cheap, chiral starting material, to be utilized in this capacity. The second part of the project dealt with modifying the carbon-carbon bond forming Suzuki reaction, which is utilized quite often as a means of combining molecular sub units in total synthesis applications. As previously stated the first area of the project was to develop high value chirons from D-glucose, but the mechanism of their formation was also investigated. The free radical initiated oxidative fragmentation of benzylidene acetals was investigated through the use of several test-case substrates in order to unravel the possible mechanistic pathways. This was performed by reacting the different acetals with N-bromosuccinimide and benzoyl peroxide in chlorobenzene at 70^C in all cases. Of the three mechanistic pathways discussed in the literature, it was determined, from the various reaction products obtained, that the fragmentation of the initial benzylic radical does not occur spontaneously but rather, oxidation proceeds to give the benzyl bromide, which then fragments via a polar pathway. It was also discovered that the regioselectivity of the fragmentation step could be altered through incorporation of an allylic system into the benzylidene acetal. This allows for the acquisition of a new set of densely functionalized. chiral, valuable synthetic intermediates in only a few steps and in high yields from a-Dglucose. The second part of the project was the utilization of the phosphonium salt room temperature ionic liquid tetradecyltrihexylphosphonium chloride (THPC) as an efficient reusable medium for the palladium catalyzed Suzuki cross-coupling reaction of aryl halides, including aryl chlorides, under mild conditions. The cross-coupling reactions were found to proceed in THPC containing small amounts of water and toluene using potassium phosphate and 1% Pd2(dba)3. Variously substituted iodobenzenes, including electron rich derivatives, reacted efficiently in THPC with a variety of arylboronic acids and afforded complete conversion within 1 hour at 50 ^C. The corresponding aryl bromides also reacted under these conditions with the addition of a catalytic amount of triphenylphosphine that allowed for complete conversion and high isolated yields. The reactions involving aryl chlorides were considerably slower, although the addition of triphenylphosphine and heating at 70 ^C allowed high conversion of electron deficient derivatives. Addition of water and hexane to the reaction products results in a triphasic system in which the top hexane phase contained the biaryl products, the palladium catalyst remained fully dissolved in the central THPC layer, while the inorganic salts were extracted into the lower aqueous phase. The catalyst was then recycled by removing the top and bottom layers and adding the reagents to the ionic liquid which was heated again at 50 ^C; resulting in complete turnover of iodobenzene. Repetition of this procedure gave the biphenyl product in 82-97% yield (repeated five times) for both the initial and recycled reaction sequences.

Reality status evaluations in mediated experiences /

This paper explores the cognitive functions of the Reality Status Evaluation (RSE) system in our experiences of narrative mediated messages (NMM) (fictional, narrative, audio-visual one-way input and moving picture messages), such as fictional TV programs and films. We regard reality in mediated experiences as a special mental and emotional construction and a multi-dimensional concept. We argue that viewers' reality sense in NMM is influenced by many factors with "real - on" as the default value. Some of these factors function as primary mental processes, including the content realism factors of those messages such as Factuality (F), Social Realism (SR), Life Relevance (LR), and Perceptual Realism - involvement (PR), which would have direct impacts on reality evaluations. Other factors, such as Narrative Meaning (NM), Emotional Responses, and personality trait Absorption (AB), will influence the reality evaluations directly or through the mediations of these main dimensions. I designed a questionnaire to study this theoretical construction. I developed items to form scales and sub-scales measuring viewers' subjective experiences of reality evaluations and these factors. Pertinent statistical techniques, such as internal consistency and factorial analysis, were employed to make revisions and improve the quality of the questionnaire. In the formal experiment, after viewing two short films, which were selected as high or low narrative structure messages from previous experiments, participants were required to answer the questionnaire, Absorption questionnaire, and SAM (Self-Assessment Manikin, measuring immediate emotional responses). Results were analyzed using the EQS, structural equation modeling (SEM), and discussed in terms oflatent relations among these subjective factors in mediated experience. The present results supported most of my theoretical hypotheses. In NMM, three main jactors, or dimensions, could be extracted in viewers' subjective reality evaluations: Social Realism (combining with Factuality), Life Relevance and Perceptual Realism. I designed two ways to assess viewers' understanding of na"ative meanings in mediated messages, questionnaire (NM-Q) and rating (NM-R) measurement, and its significant influences on reality evaluations was supported in the final EQS models. Particularly in high story stnlcture messages, the effect of Narrative Meaning (NM) can rarely be explained by only these dimensions of reality evaluations. Also, Empathy seems to playa more important role in RSE of low story structure messages. Also, I focused on two other factors that were pertinent to RSE in NMM, the personality trait Absorption, and Emotional Responses (including two dimensions: Valence and Intensity). Final model results partly supported my theoretical hypotheses about the relationships among Absorption (AB), Social Realism (SR) and Life Relevance (LR); and the immediate impact of Emotional Responses on Perceptual Realism cPR).