New Reactivity of High Oxidation State Palladium Complexes.

New methodology involving Pd-mediated catalysis that proposes Pd(II/IV) mechanisms has exploded over the past decade. Despite the implication of Pd(IV) intermediates prior to bond-forming C–X reductive elimination in these catalytic reactions, the reported organometallic Pd(IV) complexes in the literature primarily underwent C–C bond-forming reductive elimination. The goal of this dissertation was to design systems to study C–X reductive elimination from observable Pd(IV) complexes. In addition to reductive elimination reactions from Pd(IV), we sought to explore other organometallic reactions at Pd(IV) centers such as C–H activation. The first data chapter presents a detailed mechanistic study of C–O and C–C bond-formation from isolable PdIV complexes. A variety of complexes were synthesized to explore how electronic factors, activation parameters, solvent effects and additive effects are involved in/influence C–O reductive elimination from a PdIV center. Additionally, we identified a system that yielded competing C–O and C–C reductive elimination from PdIV. Therefore, we conducted mechanistic studies to probe C–C bond formation from PdIV; we were able to propose a mechanism for this transformation as well. Chapter 3 investigates sp2 versus sp3-C–X bond formation from PdIV complexes. Interestingly, in all of the systems that were studied, sp3-C–X bond formation out competes sp2 reductive elimination. This chapter presents novel examples of sp3-C–F, C–N and C–O reductive elimination from PdIV in addition to sp3-C–Cl bond-formation. These reactions represent the first examples of high yielding sp3-C–X reductive elimination from PdIV. Lastly, the mechanistic insights gained from these studies lead us to examine systems for sp3-C–X bond-formation that do not use the oxidant to deliver the desired functionality. Next, Chapter 4 of this thesis describes the development a ligand system to explore C–H activation directly at a PdIV center. We designed a complex where reductive elimination is slow and C–H activation is observed. This enabled us to compare the selectively of C–H activation at a PdIV center versus a PdII center. Finally, the thesis concludes with a discussion of the future for the development of PdIV chemistry.Ph.D.ChemistryUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/91616/1/racowski_1.pd

Survey of the wheat and derivatives production chain regarding the 2030 Agenda and the SDG

The adequacy of the 2030 Agenda and the SDG is a new instrument that companies should implement within their innovative processes to improve social, environmental, and economic issues internally and externally. Thus, this work aims to diagnose the wheat and derivatives segment and the adoption/implementation of the 2030 Agenda and SDG to business practices. To this end, a sample of 91 companies of the wheat agribusiness and processing industry was studied, using the survey-based exploratory-descriptive methodology. Data collected underwent qualitative and quantitative analysis, which demonstrated that although many of the SDGs are under assessment for possible new integration with those remaining and those under implementation, the number of objectives already included in business practices is still trivial (38.4%, that is, about 6 out of 17).The adequacy of the 2030 Agenda and the SDG is a new instrument that companies should implement within their innovative processes to improve social, environmental, and economic issues internally and externally. Thus, this work aims to diagnose the wheat and derivatives segment and the adoption/implementation of the 2030 Agenda and SDG to business practices. To this end, a sample of 91 companies of the wheat agribusiness and processing industry was studied, using the survey-based exploratory-descriptive methodology. Data collected underwent qualitative and quantitative analysis, which demonstrated that although many of the SDGs are under assessment for possible new integration with those remaining and those under implementation, the number of objectives already included in business practices is still trivial (38.4%, that is, about 6 out of 17)

Carbon(sp 3 )Fluorine Bond‐Forming Reductive Elimination from Palladium(IV) Complexes

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/90520/1/ange_201107816_sm_miscellaneous_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/90520/2/3470_ftp.pd

Carbon(sp 3 )Fluorine Bond‐Forming Reductive Elimination from Palladium(IV) Complexes

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/90585/1/anie_201107816_sm_miscellaneous_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/90585/2/3414_ftp.pd

Concerted reductive coupling of an alkyl chloride at Pt(IV)

Oxidation of a doubly cyclometallated platinum(II) complex results in two isomeric platinum(IV) complexes. Whereas the trans isomer is robust, being manipulable in air at room temperature, the cis isomer decomposes at −20 °C and above. Reductive coupling of an alkyl chloride at the cis isomer gives a new species which can be reoxidised. The independence of this coupling on additional halide rules out the reverse of an SN2 reaction, leaving a concerted process as the only sensible reaction pathway

Desenvolvimento de bebida à base de amendoim (Arachis Hypogaea) com adição de fibras e estabilizada com hidrocolóides / Development of peanut-based drink (Arachis Hypogaea) with added fibers and stabilized with hydrocolloids

Levando-se em consideração a crescente busca por alimentos saudáveis e a mudança de hábitos alimentares, como o veganismo, a produção de extratos vegetais se torna necessária para atender essa parcela do mercado, além de ser uma alternativa importante para as pessoas intolerantes à lactose ou alérgicas à proteína do leite. O presente trabalho teve como objetivo elaborar uma bebida à base de extrato de amendoim sendo fonte de fibras, pela adição da goma arábica, e estabilizada com hidrocolóides (gomas guar e xantana). Para o preparo da bebida, os grãos previamente torrados foram triturados, em seguida foram adicionados as gomas e a água. O extrato passou por um tratamento térmico de 85°C por 3 minutos sob agitação e em seguida foi filtrado por peneira com mesh 28 (definida após análise sensorial de preferência entre aberturas de malhas 24, 28 e 32), separando o extrato líquido da torta. Para chegar a formulação ideal foi elaborado um planejamento experimental para observar a interação das gomas em relação aos sólidos e a sua estabilidade. A partir dos resultados obtidos foram testadas formulações com diferentes concentrações (0,01; 0,02; 0,03; 0,04; 0,05%) das gomas xantana e guar e as amostras que se mantiveram estáveis durante 24h sob refrigeração foram submetidas a análise sensorial de ordenação e aceitação global e intenção de compra. As amostras preferidas foram as com 0,04 e 0,05% de concentração e, visando a viabilidade econômica do projeto, foi escolhida a formulação com 0,04% para determinar a composição centesimal do produto. A avaliação sensorial mostrou que a bebida teve boa aceitação global (8±1) pelos provadores e intenção de compra de 73%, além de obter 1,5% de fibras na sua composição, podendo ser considerada como fonte de fibras na porção

Palladium–mediated organofluorine chemistry

Producción CientíficaThe substitution of fluorine for hydrogen in a molecule may result in profound changes in its properties and behaviour. Fluorine does not introduce special steric constraints since the F atom has a small size. However, the changes in bond polarity and the possibility of forming hydrogen bonds with other hydrogen donor fragments in the same or other molecules, may change the solubility and physical properties of the fluorinated compound when compared to the non-fluorinated one. Fluorine forms strong bonds to other elements and this ensures a good chemical stability. Altogether, fluorinated compounds are very attractive in materials chemistry and in medicinal chemistry, where many biologically active molecules and pharmaceuticals do contain fluorine in their structure and this has been shown to be essential for their activityJunta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA302U13)Junta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA256U13