{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84376"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84376","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Investigation of the Stereochemistry of the Methyl-to-Methylene Elimination in the Biosynthesis of Several Terpenes Through the Use of Chiral Methyl Labeled Compounds","abstract":"The synthesis of (R)- (13-$\\sp2$H, $\\sp3$H) farnesyl diphosphate has been completed by methodology similar to that used for the synthesis of (R)- (9-$\\sp2$H, $\\sp3$H) geranyl diphosphate. Incubation of the radiolabeled farnesyl diphosphate with 5-epi-aristolochene synthase gave the ($\\sp2$H, $\\sp3$H) olefin in a 10% radiochemical yield. Analysis by $\\sp3$H NMR spectroscopy showed 3 peaks in a 5:1:0.7 ratio which correspond to the (12-$\\sp2$H, $\\sp3$H) -, (12-$\\sp1$H, $\\sp3$H) -, and (1-$\\sp3$H, 12-$\\sp2$H) 5-epi-aristolochene, respectively. However, the assignment of these peaks and the determination of the facial selectivity of the enzyme were not possible owing to the lack of a reference sample of 5-epi-aristolochene for NMR comparisons and NOE experiments.","abstract_html":"The synthesis of (R)- (13-$\\sp2$H, $\\sp3$H) farnesyl diphosphate has been completed by methodology similar to that used for the synthesis of (R)- (9-$\\sp2$H, $\\sp3$H) geranyl diphosphate. Incubation of the radiolabeled farnesyl diphosphate with 5-epi-aristolochene synthase gave the ($\\sp2$H, $\\sp3$H) olefin in a 10% radiochemical yield. Analysis by $\\sp3$H NMR spectroscopy showed 3 peaks in a 5:1:0.7 ratio which correspond to the (12-$\\sp2$H, $\\sp3$H) -, (12-$\\sp1$H, $\\sp3$H) -, and (1-$\\sp3$H, 12-$\\sp2$H) 5-epi-aristolochene, respectively. However, the assignment of these peaks and the determination of the facial selectivity of the enzyme were not possible owing to the lack of a reference sample of 5-epi-aristolochene for NMR comparisons and NOE experiments.","abstract_has_math":true,"creators":["Elmore, Charles Sherman"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Coates, R.M."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:14:12Z","date_published":"2015-09-25T22:14:12Z","updated_at":"2026-07-22T22:26:23Z","subjects":["Chemistry, Biochemistry"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI9812580"],"render_values":[{"text":"(MiAaPQ)AAI9812580","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84376","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Coates, R.M."]},{"key":"dc:creator","label":"Author","values":["Elmore, Charles Sherman"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:14:12Z","10000-01-01","1997"]},{"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, Biochemistry"]}]},{"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/2142/84376","(MiAaPQ)AAI9812580"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The synthesis of (R)- (13-$\\sp2$H, $\\sp3$H) farnesyl diphosphate has been completed by methodology similar to that used for the synthesis of (R)- (9-$\\sp2$H, $\\sp3$H) geranyl diphosphate. Incubation of the radiolabeled farnesyl diphosphate with 5-epi-aristolochene synthase gave the ($\\sp2$H, $\\sp3$H) olefin in a 10% radiochemical yield. Analysis by $\\sp3$H NMR spectroscopy showed 3 peaks in a 5:1:0.7 ratio which correspond to the (12-$\\sp2$H, $\\sp3$H) -, (12-$\\sp1$H, $\\sp3$H) -, and (1-$\\sp3$H, 12-$\\sp2$H) 5-epi-aristolochene, respectively. However, the assignment of these peaks and the determination of the facial selectivity of the enzyme were not possible owing to the lack of a reference sample of 5-epi-aristolochene for NMR comparisons and NOE experiments.","Made available in DSpace on 2015-09-25T22:14:12Z (GMT). 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Incubation of the radiolabeled farnesyl diphosphate with 5-epi-aristolochene synthase gave the ($\\sp2$H, $\\sp3$H) olefin in a 10% radiochemical yield. Analysis by $\\sp3$H NMR spectroscopy showed 3 peaks in a 5:1:0.7 ratio which correspond to the (12-$\\sp2$H, $\\sp3$H) -, (12-$\\sp1$H, $\\sp3$H) -, and (1-$\\sp3$H, 12-$\\sp2$H) 5-epi-aristolochene, respectively. However, the assignment of these peaks and the determination of the facial selectivity of the enzyme were not possible owing to the lack of a reference sample of 5-epi-aristolochene for NMR comparisons and NOE experiments.","Made available in DSpace on 2015-09-25T22:14:12Z (GMT). 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