{"id":{"repo_id":"texas","oai_identifier":"oai:repositories.lib.utexas.edu:2152/19501"},"canonical_url":"https://search.dev.ndltd.org/etd/texas/oai:repositories.lib.utexas.edu:2152/19501","repository":{"repo_id":"texas","name":"University of Texas","base_url":"https://repositories.lib.utexas.edu/server/oai/request"},"display":{"title":"Enantioselective synthesis of 2,2,5-Tri- and 2,2,5,5-tetrasubstituted tetrahydrofurans and synthesis of diketopiperazine containing natural products","abstract":"A chiral vinyl sulfoxide has been developed that undergoes highly diastereoselective Diels−Alder cycloadditions with various substituted furans in excellent yield. The cycloadducts can be stereoselectively transformed into tetrasubstituted tetrahydrofurans via ring-opening metathesis/cross-metathesis or oxidative cleavage and refunctionalization. A partial synthesis of the bioactive diketopiperazine containing natural product gliocladin C was achieved in nine steps, and 13.4% overall yield. The synthesis featured several novel transformations including the construction of the core structure by an elimination and nucleophilic addition sequence, followed by a Lewis acid promoted coupling with indole giving the key quaternary oxindole intermediate. A new protocol for intramolecular reductive coupling of the oxoindole and bis-unsaturated diketopiperazine led to successful construction of the hexacyclic skeleton.","abstract_html":"A chiral vinyl sulfoxide has been developed that undergoes highly diastereoselective Diels−Alder cycloadditions with various substituted furans in excellent yield. The cycloadducts can be stereoselectively transformed into tetrasubstituted tetrahydrofurans via ring-opening metathesis/cross-metathesis or oxidative cleavage and refunctionalization. A partial synthesis of the bioactive diketopiperazine containing natural product gliocladin C was achieved in nine steps, and 13.4% overall yield. The synthesis featured several novel transformations including the construction of the core structure by an elimination and nucleophilic addition sequence, followed by a Lewis acid promoted coupling with indole giving the key quaternary oxindole intermediate. A new protocol for intramolecular reductive coupling of the oxoindole and bis-unsaturated diketopiperazine led to successful construction of the hexacyclic skeleton.","abstract_has_math":false,"creators":["Benjamin, Noah Meyer"],"institution":"The University of Texas at Austin","degree_name":"Doctor of Philosophy","degree_level":"Doctoral","degree_discipline":"Organic Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":["Martin, Stephen F"],"committee_chairs":[],"committee_members":["Krische, Michael J","Iverson, Brent L","Brodbelt, Jennifer S","Kerwin, Sean M","Bielawski, Christopher W"],"year":2012,"date_issued":"2012-12","date_published":"2012-12","updated_at":"2026-07-24T05:01:00Z","subjects":["Diketopiperazine, Tetrahydrofuran, Noah Benjamin"],"languages":["en_US"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2152/19501","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Martin, Stephen F"]},{"key":"dc:contributor.committeemember","label":"Committee Member","values":["Krische, Michael J","Iverson, Brent L","Brodbelt, Jennifer S","Kerwin, Sean M","Bielawski, Christopher W"]},{"key":"dc:creator","label":"Author","values":["Benjamin, Noah Meyer"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2013-02-18T19:55:27Z"]},{"key":"dc:date.issued","label":"Date","values":["2012-12"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Organic Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["The University of Texas at Austin"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Diketopiperazine, Tetrahydrofuran, Noah Benjamin"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en_US"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/2152/19501"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["text"]},{"key":"dc:description.abstract","label":"Abstract","values":["A chiral vinyl sulfoxide has been developed that undergoes highly diastereoselective Diels−Alder cycloadditions with various substituted furans in excellent yield. The cycloadducts can be stereoselectively transformed into tetrasubstituted tetrahydrofurans via ring-opening metathesis/cross-metathesis or oxidative cleavage and refunctionalization. A partial synthesis of the bioactive diketopiperazine containing natural product gliocladin C was achieved in nine steps, and 13.4% overall yield. The synthesis featured several novel transformations including the construction of the core structure by an elimination and nucleophilic addition sequence, followed by a Lewis acid promoted coupling with indole giving the key quaternary oxindole intermediate. A new protocol for intramolecular reductive coupling of the oxoindole and bis-unsaturated diketopiperazine led to successful construction of the hexacyclic skeleton."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Enantioselective synthesis of 2,2,5-Tri- and 2,2,5,5-tetrasubstituted tetrahydrofurans and synthesis of diketopiperazine containing natural products"]}]}],"canonical_facts":{"dc:contributor.advisor":["Martin, Stephen F"],"dc:contributor.committeemember":["Krische, Michael J","Iverson, Brent L","Brodbelt, Jennifer S","Kerwin, Sean M","Bielawski, Christopher W"],"dc:creator":["Benjamin, Noah Meyer"],"dc:date.accessioned":["2013-02-18T19:55:27Z"],"dc:date.issued":["2012-12"],"dc:description":["text"],"dc:description.abstract":["A chiral vinyl sulfoxide has been developed that undergoes highly diastereoselective Diels−Alder cycloadditions with various substituted furans in excellent yield. The cycloadducts can be stereoselectively transformed into tetrasubstituted tetrahydrofurans via ring-opening metathesis/cross-metathesis or oxidative cleavage and refunctionalization. A partial synthesis of the bioactive diketopiperazine containing natural product gliocladin C was achieved in nine steps, and 13.4% overall yield. The synthesis featured several novel transformations including the construction of the core structure by an elimination and nucleophilic addition sequence, followed by a Lewis acid promoted coupling with indole giving the key quaternary oxindole intermediate. A new protocol for intramolecular reductive coupling of the oxoindole and bis-unsaturated diketopiperazine led to successful construction of the hexacyclic skeleton."],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["http://hdl.handle.net/2152/19501"],"dc:language.iso":["en_US"],"dc:subject":["Diketopiperazine, Tetrahydrofuran, Noah Benjamin"],"dc:title":["Enantioselective synthesis of 2,2,5-Tri- and 2,2,5,5-tetrasubstituted tetrahydrofurans and synthesis of diketopiperazine containing natural products"],"thesis:degree_discipline":["Organic Chemistry"],"thesis:degree_level":["Doctoral"],"thesis:degree_name":["Doctor of Philosophy"],"thesis:institution_name":["The University of Texas at Austin"]},"updated_at":"2026-07-24T05:01:00Z"}