{"id":{"repo_id":"cuny","oai_identifier":"oai:academicworks.cuny.edu:cc_etds_theses-1612"},"canonical_url":"https://search.dev.ndltd.org/etd/cuny/oai:academicworks.cuny.edu:cc_etds_theses-1612","repository":{"repo_id":"cuny","name":"City University of New York - City College","base_url":"https://academicworks.cuny.edu/do/oai/"},"display":{"title":"JULIA-KOCIENSKI APPROACH TO 4-SUBSTITUTED 1- ALKENYL-1H-1,2,3-TRIAZOLES","abstract":"<p>A modular approach to the synthesis of 4-substituted N-vinyltriazoles was<br />developed. The triazole cores were assembled by copper-catalyzed 1,3-dipolar<br />cycloaddition of 1-phenyl-1H-tetrazol-5-yl (PT) azidomethyl sulfide with: pmethoxyphenyl, 2-pyridyl, and triisopropylsilyl alkynes. Subsequent oxidation of the sulfides furnished 4-substituted triazoles with a Julia-Kocienski olefination handle attached at the N1 atom of the triazole. Olefination reactions of triazole-derived Julia-Kocienski reagents with paraformaldehyde gave 1-ethenyl-1H-1,2,3-triazoles. Heck reactions of these products with phenyl or p-methoxyphenyl iodide led to further functionalization of the terminal carbon, with E/Z-olefin ratios ≥ 92%. Heck reaction with p-cyanophenyl iodide gave low conversion, and that with 2-thienyl iodide did not proceed. On the other<br />hand, Julia-Kocienski olefinations proceeded with electron-rich and electron-deficient aryl, as well as alkyl aldehydes. The resulting 1,2-disubstituted alkenes were formed in good yields, but with moderate to poor E/Z-selectivities. A modular approach to the synthesis of 4-substituted N-vinyltriazoles was<br /> developed. The triazole cores were assembled by copper-catalyzed 1,3-dipolar<br /> cycloaddition of 1-phenyl-1H-tetrazol-5-yl (PT) azidomethyl sulfide with: pmethoxyphenyl, 2-pyridyl, and triisopropylsilyl alkynes. Subsequent oxidation of the sulfides furnished 4-substituted triazoles with a Julia-Kocienski olefination handle attached at the N1 atom of the triazole. Olefination reactions of triazole-derived Julia-Kocienski reagents with paraformaldehyde gave 1-ethenyl-1H-1,2,3-triazoles. Heck reactions of these products with phenyl or p-methoxyphenyl iodide led to further functionalization of the terminal carbon, with E/Z-olefin ratios ≥ 92%. Heck reaction with p-cyanophenyl iodide gave low conversion, and that with 2-thienyl iodide did not proceed. On the other hand, Julia-Kocienski olefinations proceeded with electron-rich and electron-deficient aryl, as well as alkyl aldehydes. The resulting 1,2-disubstituted alkenes were formed in good yields, but with moderate to poor E/Z-selectivities.</p>","abstract_html":"&lt;p&gt;A modular approach to the synthesis of 4-substituted N-vinyltriazoles was&lt;br /&gt;developed. The triazole cores were assembled by copper-catalyzed 1,3-dipolar&lt;br /&gt;cycloaddition of 1-phenyl-1H-tetrazol-5-yl (PT) azidomethyl sulfide with: pmethoxyphenyl, 2-pyridyl, and triisopropylsilyl alkynes. Subsequent oxidation of the sulfides furnished 4-substituted triazoles with a Julia-Kocienski olefination handle attached at the N1 atom of the triazole. Olefination reactions of triazole-derived Julia-Kocienski reagents with paraformaldehyde gave 1-ethenyl-1H-1,2,3-triazoles. Heck reactions of these products with phenyl or p-methoxyphenyl iodide led to further functionalization of the terminal carbon, with E/Z-olefin ratios ≥ 92%. Heck reaction with p-cyanophenyl iodide gave low conversion, and that with 2-thienyl iodide did not proceed. On the other&lt;br /&gt;hand, Julia-Kocienski olefinations proceeded with electron-rich and electron-deficient aryl, as well as alkyl aldehydes. The resulting 1,2-disubstituted alkenes were formed in good yields, but with moderate to poor E/Z-selectivities. A modular approach to the synthesis of 4-substituted N-vinyltriazoles was&lt;br /&gt; developed. The triazole cores were assembled by copper-catalyzed 1,3-dipolar&lt;br /&gt; cycloaddition of 1-phenyl-1H-tetrazol-5-yl (PT) azidomethyl sulfide with: pmethoxyphenyl, 2-pyridyl, and triisopropylsilyl alkynes. Subsequent oxidation of the sulfides furnished 4-substituted triazoles with a Julia-Kocienski olefination handle attached at the N1 atom of the triazole. Olefination reactions of triazole-derived Julia-Kocienski reagents with paraformaldehyde gave 1-ethenyl-1H-1,2,3-triazoles. Heck reactions of these products with phenyl or p-methoxyphenyl iodide led to further functionalization of the terminal carbon, with E/Z-olefin ratios ≥ 92%. Heck reaction with p-cyanophenyl iodide gave low conversion, and that with 2-thienyl iodide did not proceed. On the other hand, Julia-Kocienski olefinations proceeded with electron-rich and electron-deficient aryl, as well as alkyl aldehydes. The resulting 1,2-disubstituted alkenes were formed in good yields, but with moderate to poor E/Z-selectivities.&lt;/p&gt;","abstract_has_math":false,"creators":["Tsetan, Kunga"],"institution":null,"degree_name":"Master of Science (M.S.)","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Barbara Zajc","Mahesh Lakshman","Urs Jans"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2016,"date_issued":"2016-01-01T08:00:00Z","date_published":"2016-01-01T08:00:00Z","updated_at":"2026-07-24T01:57:08Z","subjects":["triazole","cycloaddition","olefination","Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://academicworks.cuny.edu/cc_etds_theses/610","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Barbara Zajc","Mahesh Lakshman","Urs Jans"]},{"key":"dc:creator","label":"Author","values":["Tsetan, Kunga"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2018-08-25T07:00:00Z"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master of Science (M.S.)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["triazole","cycloaddition","olefination","Chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://academicworks.cuny.edu/cc_etds_theses/610"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["<p>A modular approach to the synthesis of 4-substituted N-vinyltriazoles was<br />developed. The triazole cores were assembled by copper-catalyzed 1,3-dipolar<br />cycloaddition of 1-phenyl-1H-tetrazol-5-yl (PT) azidomethyl sulfide with: pmethoxyphenyl, 2-pyridyl, and triisopropylsilyl alkynes. Subsequent oxidation of the sulfides furnished 4-substituted triazoles with a Julia-Kocienski olefination handle attached at the N1 atom of the triazole. Olefination reactions of triazole-derived Julia-Kocienski reagents with paraformaldehyde gave 1-ethenyl-1H-1,2,3-triazoles. Heck reactions of these products with phenyl or p-methoxyphenyl iodide led to further functionalization of the terminal carbon, with E/Z-olefin ratios ≥ 92%. Heck reaction with p-cyanophenyl iodide gave low conversion, and that with 2-thienyl iodide did not proceed. On the other<br />hand, Julia-Kocienski olefinations proceeded with electron-rich and electron-deficient aryl, as well as alkyl aldehydes. The resulting 1,2-disubstituted alkenes were formed in good yields, but with moderate to poor E/Z-selectivities. A modular approach to the synthesis of 4-substituted N-vinyltriazoles was<br /> developed. The triazole cores were assembled by copper-catalyzed 1,3-dipolar<br /> cycloaddition of 1-phenyl-1H-tetrazol-5-yl (PT) azidomethyl sulfide with: pmethoxyphenyl, 2-pyridyl, and triisopropylsilyl alkynes. Subsequent oxidation of the sulfides furnished 4-substituted triazoles with a Julia-Kocienski olefination handle attached at the N1 atom of the triazole. Olefination reactions of triazole-derived Julia-Kocienski reagents with paraformaldehyde gave 1-ethenyl-1H-1,2,3-triazoles. Heck reactions of these products with phenyl or p-methoxyphenyl iodide led to further functionalization of the terminal carbon, with E/Z-olefin ratios ≥ 92%. Heck reaction with p-cyanophenyl iodide gave low conversion, and that with 2-thienyl iodide did not proceed. On the other hand, Julia-Kocienski olefinations proceeded with electron-rich and electron-deficient aryl, as well as alkyl aldehydes. The resulting 1,2-disubstituted alkenes were formed in good yields, but with moderate to poor E/Z-selectivities.</p>"]},{"key":"dc:title","label":"Title","values":["JULIA-KOCIENSKI APPROACH TO 4-SUBSTITUTED 1- ALKENYL-1H-1,2,3-TRIAZOLES"]}]}],"canonical_facts":{"dc:contributor":["Barbara Zajc","Mahesh Lakshman","Urs Jans"],"dc:creator":["Tsetan, Kunga"],"dc:date.available":["2018-08-25T07:00:00Z"],"dc:description.abstract":["<p>A modular approach to the synthesis of 4-substituted N-vinyltriazoles was<br />developed. The triazole cores were assembled by copper-catalyzed 1,3-dipolar<br />cycloaddition of 1-phenyl-1H-tetrazol-5-yl (PT) azidomethyl sulfide with: pmethoxyphenyl, 2-pyridyl, and triisopropylsilyl alkynes. Subsequent oxidation of the sulfides furnished 4-substituted triazoles with a Julia-Kocienski olefination handle attached at the N1 atom of the triazole. Olefination reactions of triazole-derived Julia-Kocienski reagents with paraformaldehyde gave 1-ethenyl-1H-1,2,3-triazoles. Heck reactions of these products with phenyl or p-methoxyphenyl iodide led to further functionalization of the terminal carbon, with E/Z-olefin ratios ≥ 92%. Heck reaction with p-cyanophenyl iodide gave low conversion, and that with 2-thienyl iodide did not proceed. On the other<br />hand, Julia-Kocienski olefinations proceeded with electron-rich and electron-deficient aryl, as well as alkyl aldehydes. The resulting 1,2-disubstituted alkenes were formed in good yields, but with moderate to poor E/Z-selectivities. A modular approach to the synthesis of 4-substituted N-vinyltriazoles was<br /> developed. The triazole cores were assembled by copper-catalyzed 1,3-dipolar<br /> cycloaddition of 1-phenyl-1H-tetrazol-5-yl (PT) azidomethyl sulfide with: pmethoxyphenyl, 2-pyridyl, and triisopropylsilyl alkynes. Subsequent oxidation of the sulfides furnished 4-substituted triazoles with a Julia-Kocienski olefination handle attached at the N1 atom of the triazole. Olefination reactions of triazole-derived Julia-Kocienski reagents with paraformaldehyde gave 1-ethenyl-1H-1,2,3-triazoles. Heck reactions of these products with phenyl or p-methoxyphenyl iodide led to further functionalization of the terminal carbon, with E/Z-olefin ratios ≥ 92%. Heck reaction with p-cyanophenyl iodide gave low conversion, and that with 2-thienyl iodide did not proceed. On the other hand, Julia-Kocienski olefinations proceeded with electron-rich and electron-deficient aryl, as well as alkyl aldehydes. The resulting 1,2-disubstituted alkenes were formed in good yields, but with moderate to poor E/Z-selectivities.</p>"],"dc:identifier":["https://academicworks.cuny.edu/cc_etds_theses/610"],"dc:subject":["triazole","cycloaddition","olefination","Chemistry"],"dc:title":["JULIA-KOCIENSKI APPROACH TO 4-SUBSTITUTED 1- ALKENYL-1H-1,2,3-TRIAZOLES"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis"],"thesis:degree_name":["Master of Science (M.S.)"]},"updated_at":"2026-07-24T01:57:08Z"}