El presente artículo investiga los vínculos políticos y artísticos entre el poeta chileno Pablo De Rokha (seudónimo de Carlos Ignacio Díaz Loyola, 1894-1968) y el proyecto maoísta. En este se argumenta que el encuentro armónico de De Rokha con el programa revolucionario chino responde a una serie de procesos y eventos personales, locales y globales que afectaron fuertemente las perspectivas del vate sobre el arte y la política. Así, esta contribución presenta a De Rokha como un tipo de revolucionario latinoamericano que se identificó con las ideas políticas y artísticas de Mao Zedong (1894-1976), basado en los problemas, experiencias y anhelos mutuos de ambas regiones.

This paper researches the political and artistic links between the Chilean poet Pablo De Rokha (pen name for Carlos Ignacio Díaz Loyola, 1894-1968) and the Maoist project. It argues that De Rokha’s harmonic encounter with the Chinese revolutionary program responds to a series of personal, local and global processes and events that strongly affected the poet’s perspectives on art and politics. This contribution then introduces De Rokha as a Latin American revolutionary who identified with the political and artistic ideas of Mao Zedong 毛澤東 (1894-1976), based on the mutual problems, experiences, and aspirations of both regions.

This thesis examines the organization of the 1970 and 1986 World Cup in Mexico. By implementing an ecology model, it demonstrates the connections between these events and the 1968 Olympic Games. This thesis argues that the hosting of the World Cup exemplified the PRI’s diminishing interest in the potential of professional sports to promote a nationalist project, and the rising influence of sporting entrepreneurs over these activities. Emilio Azcarrága Milmo and Guillermo Cañedo became the driving figures behind the hosting of the 1970 and the 1986 World Cups from their position as leaders of the Mexican soccer federation and Mexico’s telecommunications company. Together, they worked to pursue and organize the World Cup with the objective of making significant profits.

This dissertation describes synthetic endeavors aimed at harnessing the reactivity of arynes and cyclic alkynes toward the synthesis of heterocycles. Arynes and cyclic alkynes are highly reactive intermediates that act as electrophilic arene and alkyne surrogates. Additionally, this dissertation outlines the strategic activation of the amide C–N bond using nickel catalysis. This recently discovered mode of reactivity is employed for the generation of molecular complexity.

Chapter One describes a systematic experimental and computational study of a particularly important class of arynes, 3-halobenzynes. Our efforts show that aryne distortion, rather than steric factors or charge distribution, are responsible for the regioselectivities observed in 3-halobenzyne trapping reactions. Experiments also validate the synthetic utility of 3-halobenzynes for the synthesis of heterocycles, using a tandem aryne trapping / cross-coupling sequence involving 3-chlorobenzyne.

Chapter Two outlines synthetic studies pertaining to two heterocyclic aryne intermediates: the 2,3-pyridyne and the 4,5-pyrimidyne. 2,3-pyridyne generation and trappings were used to access a variety of functionalized pyridines in a regioselective manner. Additionally, synthetic routes to two isomeric silyl triflates, which were intended to serve as precursors to the 4,5-pyrimidyne, are disclosed. Subsequent 4,5-pyrimidyne generation and trapping experiments were ultimately unfruitful.

Chapter Three reports on the synthesis of poly(benzonorbornadiene) polymers via a strategic blend of benzyne chemistry and ROMP. Through a comparative study, we demonstrate that substitution at the benzylic / allylic position prevents oxidative deformation and polymer decomposition, yet does not inhibit polymerization by common ruthenium catalysts with good control over molecular weight dispersity.

Chapter Four illustrates the strategic use of cyclohexyne and the more elusive intermediate, cyclopentyne, as efficient tools for the synthesis of new heterocyclic compounds with high sp3 character. Experimental and computational studies of the first 3-substituted cyclohexyne are also described. The observed regioselectivities are explained by the distortion / interaction model.

Chapter Five describes the generation of the first 3,4-piperidyne and its use as a building block for the synthesis of highly decorated piperidines. Experimental and computational studies of this intermediate are disclosed, along with comparisons to the well-known 3,4-pyridyne aromatic analogue. Additionally, the distortion / interaction model is used to explain the observed regioselectivities.

Chapter Six pertains to the generation of two stained oxacyclic intermediates, the 4,5-benzofuranyne and the 3,4-oxacyclohexyne. In situ trapping of these intermediates affords an array of heterocyclic scaffolds. Across all trapping reactions performed, product distributions are consistent with predictions made with the distortion / interaction model. Oxygen-containing strained intermediates were also found to react with higher selectivities when compared to their corresponding nitrogen-containing analogues.

Chapter Seven depicts the first non-decarbonylative Mizoroki–Heck reactions of amide derivatives. The transformation relies on the use of nickel catalysis and proceeds with sterically hindered tri- and tetrasubstituted olefins to yield products containing quaternary centers. Moreover, a diastereoselective variant of this reaction demonstrates its utility for accessing adducts bearing vicinal stereocenters. Our results demonstrate that amide derivatives can be used as building blocks for the assembly of complex scaffolds.

Elucidating the genetic modifications that contributed to the evolution of neurodevelopmental features unique to the human lineage has proved challenging. The rise in the availability of higher-quality primate genomes has allowed researchers to perform comparisons to identify genetic variation exclusively found in humans. Such analyses have highlighted different types of genetic variants as potential drivers in species differentiation within primates, where segmental duplications have gained particular attention given the overall increase in duplicated bases observed in primate genomes and the known potential of duplicated genes to gain novel functions. Therefore, recent surveys of human and non-human primate genomes have identified segmental duplications exclusively found in humans that contain genes with protein-coding gene paralogs that are clustered in genomic regions associated with human neurological conditions, making them top candidates for further functional studies. Since there are 30 gene families included in these human-specific segmental duplications, there is a need for higher-throughput and robust methods to functionally screen these genes to highlight candidates for more detailed molecular investigations. To address this need, we propose zebrafish as a model organism with ideal characteristics to screen candidate human-specific duplicated genes potentially impacting neurodevelopment. We first performed a thorough evaluation of current tools for gene editing in zebrafish and define a set of recommendations for general genetic screenings using zebrafish as a model, with a particular focus on the description of cost-efficient methods that provide consistent results across experiments. Then, we optimized a high-throughput phenotyping pipeline that includes rapid morphological and behavioral assessments, which we validated using generated mutants of known genes associated with several neurological conditions. Applying this information, we used zebrafish to functionally test a human-specific duplicated gene with comprehensive studies in mouse (SRGAP2) as a proof-of-concept. Our zebrafish srgap2 knockouts and SRGAP2C-humanized exhibited alterations in the expression of axogenesis-related genes and an imbalance in neuronal populations likely increasing their susceptibility to seizures, all results that are consistent with the findings in mice models. In addition, our data points to a potential novel function never-before-reported for this gene in visual system development. Building off the success of SRGAP2, we expanded our functional screen to an additional nine human-specific duplicated genes using a pipeline that combines CRISPR-based gene editing, temporal expression of human genes, phenotyping platforms, and cellular evaluations at single-cell resolution. This allowed us to highlight candidate genes consistently exhibiting alterations in zebrafish neurodevelopment, warranting follow-up with more detailed molecular functional studies to link these genes to the evolution of human-unique neurological features. Broadly speaking, this dissertation includes a framework to establish zebrafish as an effective model for functional evaluations of genes important in human neurodevelopment using optimized methods.