{"id":{"repo_id":"central-wash","oai_identifier":"oai:digitalcommons.cwu.edu:etd-1712"},"canonical_url":"https://search.dev.ndltd.org/etd/central-wash/oai:digitalcommons.cwu.edu:etd-1712","repository":{"repo_id":"central-wash","name":"Central Washington University","base_url":"https://digitalcommons.cwu.edu/do/oai/"},"display":{"title":"Chemoselective and Stereoselective Exploration of the Chemical Reactivity Space of Castagnoli-Cushman-Derived Allylic Lactamoyl Esters: Application to the Synthesis of Aza-Polycyclic Architectures","abstract":"The synthesis and evaluation of structure-activity relationships of saturated nitrogen heterocycles is the focal point of various pharmaceutical companies thanks to the high biological activity of previously isolated azacycles. Here, we describe an operationally simple and highly efficient approach to macrocyclic lactams bearing vicinal stereocenters and a challenging cycloalkyne motif. The outcomes are achieved through a novel [4 + 2] cycloaddition reaction between an <em>N</em>-iodoarylated-1,3-azadiene and cyclic anhydrides, followed by interception of the cycloadducts in cross-coupling manifolds (<em>e.g.</em>, Sonogashira coupling) and concomitant lithiation-cyclization of the tethered alkyne. An unprecedented example of a hydroamino alkylation that is transition metal-free and occurs at room temperature will also be discussed.","abstract_html":"The synthesis and evaluation of structure-activity relationships of saturated nitrogen heterocycles is the focal point of various pharmaceutical companies thanks to the high biological activity of previously isolated azacycles. Here, we describe an operationally simple and highly efficient approach to macrocyclic lactams bearing vicinal stereocenters and a challenging cycloalkyne motif. The outcomes are achieved through a novel [4 + 2] cycloaddition reaction between an &lt;em&gt;N&lt;/em&gt;-iodoarylated-1,3-azadiene and cyclic anhydrides, followed by interception of the cycloadducts in cross-coupling manifolds (&lt;em&gt;e.g.&lt;/em&gt;, Sonogashira coupling) and concomitant lithiation-cyclization of the tethered alkyne. An unprecedented example of a hydroamino alkylation that is transition metal-free and occurs at room temperature will also be discussed.","abstract_has_math":false,"creators":["Mansker, Brandon Joseph"],"institution":null,"degree_name":"Master of Science (MS)","degree_level":null,"degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Timothy K. 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Here, we describe an operationally simple and highly efficient approach to macrocyclic lactams bearing vicinal stereocenters and a challenging cycloalkyne motif. The outcomes are achieved through a novel [4 + 2] cycloaddition reaction between an <em>N</em>-iodoarylated-1,3-azadiene and cyclic anhydrides, followed by interception of the cycloadducts in cross-coupling manifolds (<em>e.g.</em>, Sonogashira coupling) and concomitant lithiation-cyclization of the tethered alkyne. An unprecedented example of a hydroamino alkylation that is transition metal-free and occurs at room temperature will also be discussed."]},{"key":"dc:title","label":"Title","values":["Chemoselective and Stereoselective Exploration of the Chemical Reactivity Space of Castagnoli-Cushman-Derived Allylic Lactamoyl Esters: Application to the Synthesis of Aza-Polycyclic Architectures"]}]}],"canonical_facts":{"dc:contributor":["Timothy K. Beng","Levente Fabry-Asztalos","Gil Belofsky"],"dc:creator":["Mansker, Brandon Joseph"],"dc:date.available":["2019-08-02T07:00:00Z"],"dc:description.abstract":["The synthesis and evaluation of structure-activity relationships of saturated nitrogen heterocycles is the focal point of various pharmaceutical companies thanks to the high biological activity of previously isolated azacycles. Here, we describe an operationally simple and highly efficient approach to macrocyclic lactams bearing vicinal stereocenters and a challenging cycloalkyne motif. The outcomes are achieved through a novel [4 + 2] cycloaddition reaction between an <em>N</em>-iodoarylated-1,3-azadiene and cyclic anhydrides, followed by interception of the cycloadducts in cross-coupling manifolds (<em>e.g.</em>, Sonogashira coupling) and concomitant lithiation-cyclization of the tethered alkyne. An unprecedented example of a hydroamino alkylation that is transition metal-free and occurs at room temperature will also be discussed."],"dc:identifier":["https://digitalcommons.cwu.edu/etd/704"],"dc:language":["English"],"dc:subject":["organic","heterocycle","synthesis","DOS","intermediates","Chemical Actions and Uses","Heterocyclic Compounds","Medicinal and Pharmaceutical Chemistry","Organic Chemicals","Polycyclic Compounds"],"dc:title":["Chemoselective and Stereoselective Exploration of the Chemical Reactivity Space of Castagnoli-Cushman-Derived Allylic Lactamoyl Esters: Application to the Synthesis of Aza-Polycyclic Architectures"],"dc:type":["Text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_name":["Master of Science (MS)"]},"updated_at":"2026-07-24T01:37:04Z"}