{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/43776"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/43776","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Direct synthesis of pyridine and pyrimidine derivatives","abstract":"I. Synthesis of Substituted Pyridine Derivatives via the Ruthenium-Catalyzed Cycloisomerization of 3-Azadienynes. The two-step conversion of various N-vinyl and N-aryl amides to the corresponding substituted pyridines and quinolines, respectively, is described. The process involves the direct conversion of amides, including sensitive N-vinyl amides, to the corresponding trimethylsilyl alkynyl imines followed by a ruthenium-catalyzed protodesilylation and cycloisomerization. A wide range of new alkynyl imines are prepared and readily converted to the corresponding azaheterocycles. II. Single-Step Synthesis of Pyrimidine Derivatives. The single-step conversion of various N-vinyl and N-aryl amides to the corresponding pyrimidine and quinazoline derivatives, respectively, is described. The process involves amide activation with 2-chloropyridine and trifluoromethanesulfonic anhydride followed by nitrile addition into the reactive intermediate and cycloisomerization. In situ nitrile generation from primary amides allows for their use as nitrile surrogates. The use of this chemistry with sensitive N-vinyl amides and epimerizable substrates in addition to a wide range of functional groups is noteworthy. III. Direct Synthesis of Pyridine Derivatives. The single-step conversion of various N-vinyl and N-aryl amides to the corresponding pyridine and quinoline derivatives, respectively, is described. The process involves amide activation with trifluoromethanesulfonic anhydride in the presence of 2-chloropyridine followed by t-nucleophile addition to the activated intermediate and annulation. Compatibility of this chemistry with sensitive N-vinyl amides, epimerizable substrates, and a variety of functional groups is noteworthy.","abstract_html":"I. Synthesis of Substituted Pyridine Derivatives via the Ruthenium-Catalyzed Cycloisomerization of 3-Azadienynes. The two-step conversion of various N-vinyl and N-aryl amides to the corresponding substituted pyridines and quinolines, respectively, is described. The process involves the direct conversion of amides, including sensitive N-vinyl amides, to the corresponding trimethylsilyl alkynyl imines followed by a ruthenium-catalyzed protodesilylation and cycloisomerization. A wide range of new alkynyl imines are prepared and readily converted to the corresponding azaheterocycles. II. Single-Step Synthesis of Pyrimidine Derivatives. The single-step conversion of various N-vinyl and N-aryl amides to the corresponding pyrimidine and quinazoline derivatives, respectively, is described. The process involves amide activation with 2-chloropyridine and trifluoromethanesulfonic anhydride followed by nitrile addition into the reactive intermediate and cycloisomerization. In situ nitrile generation from primary amides allows for their use as nitrile surrogates. The use of this chemistry with sensitive N-vinyl amides and epimerizable substrates in addition to a wide range of functional groups is noteworthy. III. Direct Synthesis of Pyridine Derivatives. The single-step conversion of various N-vinyl and N-aryl amides to the corresponding pyridine and quinoline derivatives, respectively, is described. The process involves amide activation with trifluoromethanesulfonic anhydride in the presence of 2-chloropyridine followed by t-nucleophile addition to the activated intermediate and annulation. Compatibility of this chemistry with sensitive N-vinyl amides, epimerizable substrates, and a variety of functional groups is noteworthy.","abstract_has_math":false,"creators":["Hill, Matthew D. (Matthew Dennis)"],"institution":"Massachusetts Institute of Technology","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Dept. of Chemistry.","school":null,"contributors":[],"advisors":["Mohammad Movassaghi."],"committee_chairs":[],"committee_members":[],"year":2008,"date_issued":"2008","date_published":"2008","updated_at":"2026-07-22T22:21:28Z","subjects":["Chemistry."],"languages":["eng"],"rights":["M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission."],"rights_urls":["http://dspace.mit.edu/handle/1721.1/7582"],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/1721.1/43776","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Mohammad Movassaghi."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. Dept. of Chemistry."]},{"key":"dc:contributor.other","label":"Dc Contributor Other","values":["Massachusetts Institute of Technology. Dept. of Chemistry."]},{"key":"dc:creator","label":"Author","values":["Hill, Matthew D. (Matthew Dennis)"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2008-12-11T18:25:52Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2008-12-11T18:25:52Z"]},{"key":"dc:date.issued","label":"Date","values":["2008"]},{"key":"dc:publisher","label":"Institution","values":["Massachusetts Institute of Technology"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry."]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission."]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://dspace.mit.edu/handle/1721.1/7582"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/1721.1/43776"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2008.","Vita.","Includes bibliographical references."]},{"key":"dc:description.abstract","label":"Abstract","values":["I. Synthesis of Substituted Pyridine Derivatives via the Ruthenium-Catalyzed Cycloisomerization of 3-Azadienynes. The two-step conversion of various N-vinyl and N-aryl amides to the corresponding substituted pyridines and quinolines, respectively, is described. The process involves the direct conversion of amides, including sensitive N-vinyl amides, to the corresponding trimethylsilyl alkynyl imines followed by a ruthenium-catalyzed protodesilylation and cycloisomerization. A wide range of new alkynyl imines are prepared and readily converted to the corresponding azaheterocycles. II. Single-Step Synthesis of Pyrimidine Derivatives. The single-step conversion of various N-vinyl and N-aryl amides to the corresponding pyrimidine and quinazoline derivatives, respectively, is described. The process involves amide activation with 2-chloropyridine and trifluoromethanesulfonic anhydride followed by nitrile addition into the reactive intermediate and cycloisomerization. In situ nitrile generation from primary amides allows for their use as nitrile surrogates. The use of this chemistry with sensitive N-vinyl amides and epimerizable substrates in addition to a wide range of functional groups is noteworthy. III. Direct Synthesis of Pyridine Derivatives. The single-step conversion of various N-vinyl and N-aryl amides to the corresponding pyridine and quinoline derivatives, respectively, is described. The process involves amide activation with trifluoromethanesulfonic anhydride in the presence of 2-chloropyridine followed by t-nucleophile addition to the activated intermediate and annulation. Compatibility of this chemistry with sensitive N-vinyl amides, epimerizable substrates, and a variety of functional groups is noteworthy."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph.D."]},{"key":"dc:title","label":"Title","values":["Direct synthesis of pyridine and pyrimidine derivatives"]}]}],"canonical_facts":{"dc:contributor.advisor":["Mohammad Movassaghi."],"dc:contributor.department":["Massachusetts Institute of Technology. Dept. of Chemistry."],"dc:contributor.other":["Massachusetts Institute of Technology. Dept. of Chemistry."],"dc:creator":["Hill, Matthew D. (Matthew Dennis)"],"dc:date.accessioned":["2008-12-11T18:25:52Z"],"dc:date.available":["2008-12-11T18:25:52Z"],"dc:date.issued":["2008"],"dc:description":["Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2008.","Vita.","Includes bibliographical references."],"dc:description.abstract":["I. Synthesis of Substituted Pyridine Derivatives via the Ruthenium-Catalyzed Cycloisomerization of 3-Azadienynes. The two-step conversion of various N-vinyl and N-aryl amides to the corresponding substituted pyridines and quinolines, respectively, is described. The process involves the direct conversion of amides, including sensitive N-vinyl amides, to the corresponding trimethylsilyl alkynyl imines followed by a ruthenium-catalyzed protodesilylation and cycloisomerization. A wide range of new alkynyl imines are prepared and readily converted to the corresponding azaheterocycles. II. Single-Step Synthesis of Pyrimidine Derivatives. The single-step conversion of various N-vinyl and N-aryl amides to the corresponding pyrimidine and quinazoline derivatives, respectively, is described. The process involves amide activation with 2-chloropyridine and trifluoromethanesulfonic anhydride followed by nitrile addition into the reactive intermediate and cycloisomerization. In situ nitrile generation from primary amides allows for their use as nitrile surrogates. The use of this chemistry with sensitive N-vinyl amides and epimerizable substrates in addition to a wide range of functional groups is noteworthy. III. Direct Synthesis of Pyridine Derivatives. The single-step conversion of various N-vinyl and N-aryl amides to the corresponding pyridine and quinoline derivatives, respectively, is described. The process involves amide activation with trifluoromethanesulfonic anhydride in the presence of 2-chloropyridine followed by t-nucleophile addition to the activated intermediate and annulation. Compatibility of this chemistry with sensitive N-vinyl amides, epimerizable substrates, and a variety of functional groups is noteworthy."],"dc:description.degree":["Ph.D."],"dc:identifier.uri":["http://hdl.handle.net/1721.1/43776"],"dc:language.iso":["eng"],"dc:publisher":["Massachusetts Institute of Technology"],"dc:rights":["M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission."],"dc:rights.uri":["http://dspace.mit.edu/handle/1721.1/7582"],"dc:subject":["Chemistry."],"dc:title":["Direct synthesis of pyridine and pyrimidine derivatives"],"dc:type":["Thesis"]},"updated_at":"2026-07-22T22:21:28Z"}