{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84097"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84097","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Chemical and Enzymatic Synthesis of Dehydropeptides and Their Fluoro Analogs","abstract":"Fluorine-substituted dehydroalanine can lead to irreversible linkages of nucleophile to dehydroalanines by an addition elimination mechanism and can be applied to the design of enzyme inhibitors and active site affinity labels. Fluorodehydroalanine has been synthesized from serine in 7 steps with a fluoro-Pummerer rearrangement as the key step. The stereochemical integrity at the alpha-carbon in the fluoro-Pummerer rearrangement was investigated and proven to be retained. Furthermore, dehydropeptides and their fluoro analogs were prepared in an enzymatic fashion. For instance, fluorinated dipeptides, L-alanine-D-fluoroalanine and L-alanine- D,L-difluoroalanine were treated with the epimerase YcjG to produce L-Ala-Dha and L-Ala-Dha(F), respectively, as determined by 1H NMR, 19F NMR and MS (ESI).","abstract_html":"Fluorine-substituted dehydroalanine can lead to irreversible linkages of nucleophile to dehydroalanines by an addition elimination mechanism and can be applied to the design of enzyme inhibitors and active site affinity labels. Fluorodehydroalanine has been synthesized from serine in 7 steps with a fluoro-Pummerer rearrangement as the key step. The stereochemical integrity at the alpha-carbon in the fluoro-Pummerer rearrangement was investigated and proven to be retained. Furthermore, dehydropeptides and their fluoro analogs were prepared in an enzymatic fashion. For instance, fluorinated dipeptides, L-alanine-D-fluoroalanine and L-alanine- D,L-difluoroalanine were treated with the epimerase YcjG to produce L-Ala-Dha and L-Ala-Dha(F), respectively, as determined by 1H NMR, 19F NMR and MS (ESI).","abstract_has_math":false,"creators":["Zhou, Hao"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["van der Donk, Wilfred A."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:12:52Z","date_published":"2015-09-25T22:12:52Z","updated_at":"2026-07-22T22:26:22Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI3070494"],"render_values":[{"text":"(MiAaPQ)AAI3070494","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84097","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["van der Donk, Wilfred A."]},{"key":"dc:creator","label":"Author","values":["Zhou, Hao"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:12:52Z","10000-01-01","2002"]},{"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"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/84097","(MiAaPQ)AAI3070494"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Fluorine-substituted dehydroalanine can lead to irreversible linkages of nucleophile to dehydroalanines by an addition elimination mechanism and can be applied to the design of enzyme inhibitors and active site affinity labels. Fluorodehydroalanine has been synthesized from serine in 7 steps with a fluoro-Pummerer rearrangement as the key step. The stereochemical integrity at the alpha-carbon in the fluoro-Pummerer rearrangement was investigated and proven to be retained. Furthermore, dehydropeptides and their fluoro analogs were prepared in an enzymatic fashion. For instance, fluorinated dipeptides, L-alanine-D-fluoroalanine and L-alanine- D,L-difluoroalanine were treated with the epimerase YcjG to produce L-Ala-Dha and L-Ala-Dha(F), respectively, as determined by 1H NMR, 19F NMR and MS (ESI).","Made available in DSpace on 2015-09-25T22:12:52Z (GMT). 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Fluorodehydroalanine has been synthesized from serine in 7 steps with a fluoro-Pummerer rearrangement as the key step. The stereochemical integrity at the alpha-carbon in the fluoro-Pummerer rearrangement was investigated and proven to be retained. Furthermore, dehydropeptides and their fluoro analogs were prepared in an enzymatic fashion. For instance, fluorinated dipeptides, L-alanine-D-fluoroalanine and L-alanine- D,L-difluoroalanine were treated with the epimerase YcjG to produce L-Ala-Dha and L-Ala-Dha(F), respectively, as determined by 1H NMR, 19F NMR and MS (ESI).","Made available in DSpace on 2015-09-25T22:12:52Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3070494.pdf: 6166113 bytes, checksum: a044ddcfcc74e081755d450d39b42168 (MD5) Previous issue date: 2002","Embargo set by: Seth Robbins for item 85378 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","131 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2002."],"dc:identifier":["http://hdl.handle.net/2142/84097","(MiAaPQ)AAI3070494"],"dc:language":["eng"],"dc:subject":["Chemistry, Organic"],"dc:title":["Chemical and Enzymatic Synthesis of Dehydropeptides and Their Fluoro Analogs"],"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":"2026-07-22T22:26:22Z"}