{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/20690"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/20690","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Total synthesis of N-(benzyloxycarbonyl)didemnin A","abstract":"Didemnin A, a cyclic depsipeptide isolated from a Caribbean tunicate, was synthesized by coupling two key fragments, (Boc-(3S,4R,5S)-Ist(TBDMS)-(2R,S;4S)-Hip-Leu-Pro-OH (Fragment I)) and (Z- scD-MeLeu-Thr(H-Me$\\sb2$Tyr)-OTMSe) (Fragment II). Fragment I was synthesized, in turn, from Boc-(3S,4R,5S)-Ist(TBDMS)-OH, Bn-(2R,S;4S)-Hip-OH, Boc- scL-Leu-OH and H- scL-Pro-OMe by stepwise elongation of the peptide chain, starting from H-Pro-OMe. Fragment II was synthesized from Z- scD-MeLeu-OH, H- scL-Thr-OMe and Boc- scL-Me$\\sb2$Tyr-OH, starting from Z- scD-MeLeu-OH. The heptapeptide Z- scD-MeLeu-Thr(Boc-(3S,4R,5S)-Ist-(2R,S;4S)-Hip-Leu-Pro-Me$\\sb2$Tyr) -OTMSe was synthesized by coupling the two fragments between proline and dimethyltyrosine using Bop-Cl. After deprotection of TMSe and Boc groups, the cyclization was accomplished between threonine and isostatine, again using Bop-Cl. The $\\sp1$H NMR and mass spectra and rotation of the synthesized N-Z-didemnin A are the same as those of natural N-Z-didemnin A.","abstract_html":"Didemnin A, a cyclic depsipeptide isolated from a Caribbean tunicate, was synthesized by coupling two key fragments, (Boc-(3S,4R,5S)-Ist(TBDMS)-(2R,S;4S)-Hip-Leu-Pro-OH (Fragment I)) and (Z- scD-MeLeu-Thr(H-Me$\\sb2$Tyr)-OTMSe) (Fragment II). Fragment I was synthesized, in turn, from Boc-(3S,4R,5S)-Ist(TBDMS)-OH, Bn-(2R,S;4S)-Hip-OH, Boc- scL-Leu-OH and H- scL-Pro-OMe by stepwise elongation of the peptide chain, starting from H-Pro-OMe. Fragment II was synthesized from Z- scD-MeLeu-OH, H- scL-Thr-OMe and Boc- scL-Me$\\sb2$Tyr-OH, starting from Z- scD-MeLeu-OH. The heptapeptide Z- scD-MeLeu-Thr(Boc-(3S,4R,5S)-Ist-(2R,S;4S)-Hip-Leu-Pro-Me$\\sb2$Tyr) -OTMSe was synthesized by coupling the two fragments between proline and dimethyltyrosine using Bop-Cl. After deprotection of TMSe and Boc groups, the cyclization was accomplished between threonine and isostatine, again using Bop-Cl. The $\\sp1$H NMR and mass spectra and rotation of the synthesized N-Z-didemnin A are the same as those of natural N-Z-didemnin A.","abstract_has_math":true,"creators":["Li, Kai-Ming"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Rinehart, Kenneth L., Jr."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T12:46:28Z","date_published":"2011-05-07T12:46:28Z","updated_at":"2026-07-22T22:25:16Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":["Copyright 1990 Li, Kai-Ming"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9114316","(UMI)AAI9114316"],"render_values":[{"text":"AAI9114316","href":null,"code":true},{"text":"(UMI)AAI9114316","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/20690","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Rinehart, Kenneth L., Jr."]},{"key":"dc:creator","label":"Author","values":["Li, Kai-Ming"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:46:28Z","10000-01-01","1990"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"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":["Chemistry, Organic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1990 Li, Kai-Ming"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9114316","(UMI)AAI9114316","http://hdl.handle.net/2142/20690"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Didemnin A, a cyclic depsipeptide isolated from a Caribbean tunicate, was synthesized by coupling two key fragments, (Boc-(3S,4R,5S)-Ist(TBDMS)-(2R,S;4S)-Hip-Leu-Pro-OH (Fragment I)) and (Z- scD-MeLeu-Thr(H-Me$\\sb2$Tyr)-OTMSe) (Fragment II). Fragment I was synthesized, in turn, from Boc-(3S,4R,5S)-Ist(TBDMS)-OH, Bn-(2R,S;4S)-Hip-OH, Boc- scL-Leu-OH and H- scL-Pro-OMe by stepwise elongation of the peptide chain, starting from H-Pro-OMe. Fragment II was synthesized from Z- scD-MeLeu-OH, H- scL-Thr-OMe and Boc- scL-Me$\\sb2$Tyr-OH, starting from Z- scD-MeLeu-OH. The heptapeptide Z- scD-MeLeu-Thr(Boc-(3S,4R,5S)-Ist-(2R,S;4S)-Hip-Leu-Pro-Me$\\sb2$Tyr) -OTMSe was synthesized by coupling the two fragments between proline and dimethyltyrosine using Bop-Cl. After deprotection of TMSe and Boc groups, the cyclization was accomplished between threonine and isostatine, again using Bop-Cl. The $\\sp1$H NMR and mass spectra and rotation of the synthesized N-Z-didemnin A are the same as those of natural N-Z-didemnin A.","Made available in DSpace on 2011-05-07T12:46:28Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9114316.pdf: 3574634 bytes, checksum: 08bc817016fa99c642f472b5a2732e87 (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:45:36Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:20:13-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Total synthesis of N-(benzyloxycarbonyl)didemnin A"]}]}],"canonical_facts":{"dc:contributor":["Rinehart, Kenneth L., Jr."],"dc:creator":["Li, Kai-Ming"],"dc:date":["2011-05-07T12:46:28Z","10000-01-01","1990"],"dc:description":["Didemnin A, a cyclic depsipeptide isolated from a Caribbean tunicate, was synthesized by coupling two key fragments, (Boc-(3S,4R,5S)-Ist(TBDMS)-(2R,S;4S)-Hip-Leu-Pro-OH (Fragment I)) and (Z- scD-MeLeu-Thr(H-Me$\\sb2$Tyr)-OTMSe) (Fragment II). Fragment I was synthesized, in turn, from Boc-(3S,4R,5S)-Ist(TBDMS)-OH, Bn-(2R,S;4S)-Hip-OH, Boc- scL-Leu-OH and H- scL-Pro-OMe by stepwise elongation of the peptide chain, starting from H-Pro-OMe. Fragment II was synthesized from Z- scD-MeLeu-OH, H- scL-Thr-OMe and Boc- scL-Me$\\sb2$Tyr-OH, starting from Z- scD-MeLeu-OH. The heptapeptide Z- scD-MeLeu-Thr(Boc-(3S,4R,5S)-Ist-(2R,S;4S)-Hip-Leu-Pro-Me$\\sb2$Tyr) -OTMSe was synthesized by coupling the two fragments between proline and dimethyltyrosine using Bop-Cl. After deprotection of TMSe and Boc groups, the cyclization was accomplished between threonine and isostatine, again using Bop-Cl. The $\\sp1$H NMR and mass spectra and rotation of the synthesized N-Z-didemnin A are the same as those of natural N-Z-didemnin A.","Made available in DSpace on 2011-05-07T12:46:28Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9114316.pdf: 3574634 bytes, checksum: 08bc817016fa99c642f472b5a2732e87 (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:45:36Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:20:13-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI9114316","(UMI)AAI9114316","http://hdl.handle.net/2142/20690"],"dc:language":["eng"],"dc:rights":["Copyright 1990 Li, Kai-Ming"],"dc:subject":["Chemistry, Organic"],"dc:title":["Total synthesis of N-(benzyloxycarbonyl)didemnin A"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:16Z"}