{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/97625"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/97625","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Progress towards the enantioselective total synthesis of trichodermamide B","abstract":"Trichodermamide B is an unusual modified dipeptide natural product, with very promising anticancer activities. While the biosynthesis of this molecule is unknown, it is proposed herein that it is formed in vivo through direct oxidation of phenylalanine to the arene oxide or arene dioxide intermediate, which is then opened via nucleophilic attack of an oxime. To probe the feasibility of this biosynthetic hypothesis, a series of bioinspired approaches to trichodermamide B have been investigated, proceeding through arene oxide equivalents. Progress towards the concise and practical total synthesis of this molecule are described herein. Notable transformations explored include the mild installation of an oxime with hydrogen atom transfer, and microbial arene oxidation to generate decagram amounts of enantiopure, value-added starting materials. This strategy has enabled rapid access to large quantities of advanced intermediates, and once complete, should afford the natural product as a single enantiomer in far fewer steps than previously reported.","abstract_html":"Trichodermamide B is an unusual modified dipeptide natural product, with very promising anticancer activities. While the biosynthesis of this molecule is unknown, it is proposed herein that it is formed in vivo through direct oxidation of phenylalanine to the arene oxide or arene dioxide intermediate, which is then opened via nucleophilic attack of an oxime. To probe the feasibility of this biosynthetic hypothesis, a series of bioinspired approaches to trichodermamide B have been investigated, proceeding through arene oxide equivalents. Progress towards the concise and practical total synthesis of this molecule are described herein. Notable transformations explored include the mild installation of an oxime with hydrogen atom transfer, and microbial arene oxidation to generate decagram amounts of enantiopure, value-added starting materials. This strategy has enabled rapid access to large quantities of advanced intermediates, and once complete, should afford the natural product as a single enantiomer in far fewer steps than previously reported.","abstract_has_math":false,"creators":["Levinn, Carolyn M"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"M.S.","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Sarlah, David"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2017,"date_issued":"2017-08-10T19:52:22Z","date_published":"2017-08-10T19:52:22Z","updated_at":"2026-07-22T22:24:34Z","subjects":["Trichodermamide B","Total synthesis","Microbial arene oxidation","Arenophile","Arene oxide"],"languages":["en"],"rights":["Copyright 2017 Carolyn Levinn"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/97625","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Sarlah, David"]},{"key":"dc:creator","label":"Author","values":["Levinn, Carolyn M"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2017-08-10T19:52:22Z","2019-08-11T09:15:28Z","2017-04-25","2017-05"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"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":["M.S."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Trichodermamide B","Total synthesis","Microbial arene oxidation","Arenophile","Arene oxide"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2017 Carolyn Levinn"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/97625"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Trichodermamide B is an unusual modified dipeptide natural product, with very promising anticancer activities. While the biosynthesis of this molecule is unknown, it is proposed herein that it is formed in vivo through direct oxidation of phenylalanine to the arene oxide or arene dioxide intermediate, which is then opened via nucleophilic attack of an oxime. To probe the feasibility of this biosynthetic hypothesis, a series of bioinspired approaches to trichodermamide B have been investigated, proceeding through arene oxide equivalents. Progress towards the concise and practical total synthesis of this molecule are described herein. Notable transformations explored include the mild installation of an oxime with hydrogen atom transfer, and microbial arene oxidation to generate decagram amounts of enantiopure, value-added starting materials. This strategy has enabled rapid access to large quantities of advanced intermediates, and once complete, should afford the natural product as a single enantiomer in far fewer steps than previously reported.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2019-05-01","The student, Carolyn Levinn, accepted the attached license on 2017-04-24 at 13:22.","The student, Carolyn Levinn, submitted this Thesis for approval on 2017-04-24 at 13:28.","This Thesis was approved for publication on 2017-04-25 at 10:16.","DSpace SAF Submission Ingestion Package generated from Vireo submission #11010 on 2017-08-10 at 14:32:31","Made available in DSpace on 2017-08-10T19:52:22Z (GMT). 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While the biosynthesis of this molecule is unknown, it is proposed herein that it is formed in vivo through direct oxidation of phenylalanine to the arene oxide or arene dioxide intermediate, which is then opened via nucleophilic attack of an oxime. To probe the feasibility of this biosynthetic hypothesis, a series of bioinspired approaches to trichodermamide B have been investigated, proceeding through arene oxide equivalents. Progress towards the concise and practical total synthesis of this molecule are described herein. Notable transformations explored include the mild installation of an oxime with hydrogen atom transfer, and microbial arene oxidation to generate decagram amounts of enantiopure, value-added starting materials. This strategy has enabled rapid access to large quantities of advanced intermediates, and once complete, should afford the natural product as a single enantiomer in far fewer steps than previously reported.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2019-05-01","The student, Carolyn Levinn, accepted the attached license on 2017-04-24 at 13:22.","The student, Carolyn Levinn, submitted this Thesis for approval on 2017-04-24 at 13:28.","This Thesis was approved for publication on 2017-04-25 at 10:16.","DSpace SAF Submission Ingestion Package generated from Vireo submission #11010 on 2017-08-10 at 14:32:31","Made available in DSpace on 2017-08-10T19:52:22Z (GMT). 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