{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/67250"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/67250","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"The Synthesis of Lauraceae Lactones: Obtusilactones, Litsenolides, and Mahubanolides","abstract":"Phenylselenenyl esters (methyl esters of 2-phenylselenenylhexadecanoic, 2-phenylselenenyloctadecanoic, and 2-phenylselenenyl-13-tetradecadienoic acids) were used as acrylate (alpha)-anion synthons in aldol addition reactions. The last acid above, bearing the terminal double bond, was synthesized by displacing the (omega)-bromide from methyl 11-bromo-2-phenylselenenylundecanoate by allyllithium. The other (alpha)-phenylselenenyl esters were made by quenching their lithium enolates with phenylselenenyl chloride. Addition to acrolein, followed by oxidation and selenoxide elimination gave the corresponding (alpha),(beta)-unsaturated esters bearing a 1-hydroxy-2-propenyl group at the (alpha)-carbon. Similarly, addition to propargylaldehyde followed by oxidative work-up gave the corresponding (alpha),(beta)-unsaturated esters bearing a 1-hydroxy-2-propynyl group at the (alpha)-carbon.","abstract_html":"Phenylselenenyl esters (methyl esters of 2-phenylselenenylhexadecanoic, 2-phenylselenenyloctadecanoic, and 2-phenylselenenyl-13-tetradecadienoic acids) were used as acrylate (alpha)-anion synthons in aldol addition reactions. The last acid above, bearing the terminal double bond, was synthesized by displacing the (omega)-bromide from methyl 11-bromo-2-phenylselenenylundecanoate by allyllithium. The other (alpha)-phenylselenenyl esters were made by quenching their lithium enolates with phenylselenenyl chloride. Addition to acrolein, followed by oxidation and selenoxide elimination gave the corresponding (alpha),(beta)-unsaturated esters bearing a 1-hydroxy-2-propenyl group at the (alpha)-carbon. Similarly, addition to propargylaldehyde followed by oxidative work-up gave the corresponding (alpha),(beta)-unsaturated esters bearing a 1-hydroxy-2-propynyl group at the (alpha)-carbon.","abstract_has_math":false,"creators":["Rollinson, Susan Lynn Wells"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-13T20:11:06Z","date_published":"2014-12-13T20:11:06Z","updated_at":"2026-07-22T22:25:57Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8108644"],"render_values":[{"text":"(UMI)AAI8108644","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/67250","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Rollinson, Susan Lynn Wells"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-13T20:11:06Z","10000-01-01","1980"]},{"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/2142/67250","(UMI)AAI8108644"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Phenylselenenyl esters (methyl esters of 2-phenylselenenylhexadecanoic, 2-phenylselenenyloctadecanoic, and 2-phenylselenenyl-13-tetradecadienoic acids) were used as acrylate (alpha)-anion synthons in aldol addition reactions. The last acid above, bearing the terminal double bond, was synthesized by displacing the (omega)-bromide from methyl 11-bromo-2-phenylselenenylundecanoate by allyllithium. The other (alpha)-phenylselenenyl esters were made by quenching their lithium enolates with phenylselenenyl chloride. Addition to acrolein, followed by oxidation and selenoxide elimination gave the corresponding (alpha),(beta)-unsaturated esters bearing a 1-hydroxy-2-propenyl group at the (alpha)-carbon. Similarly, addition to propargylaldehyde followed by oxidative work-up gave the corresponding (alpha),(beta)-unsaturated esters bearing a 1-hydroxy-2-propynyl group at the (alpha)-carbon.","Hydrolysis of the olefinic esters to the corresponding carboxylic acids followed by lactonization (iodine or phenylselenenyl chloride) and hydrogenolysis (tri-n-butyltin hydride) gave (alpha)-alkylidene-(beta)-hydroxy-(gamma)-methyl-(gamma)-butyrolactones which are known natural products (litsenolides, dihydromahubanolides). Hydrolysis of the acetylenic esters to the corresponding carboxylic acids, followed by lactonization (mercuric trifluoroacetate or sodium bicarbonate) gave (alpha)-alkylidene-(beta)-hydroxy-(gamma)-methylene (gamma)-butyrolactones which are also known natural products (obtusilactones, mahubanolides). One of these, obtusilactone, the (gamma)-methylene lactone with the (alpha)-11-dodecenylidene moiety, has been reported to be cytotoxic.","Made available in DSpace on 2014-12-13T20:11:06Z (GMT). No. of bitstreams: 1 8108644.pdf: 3438344 bytes, checksum: d807d264c2b9b0059aa1476aa5e4aa10 (MD5) Previous issue date: 1980","Embargo set by: Seth Robbins for item 67428 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","126 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1980."]},{"key":"dc:title","label":"Title","values":["The Synthesis of Lauraceae Lactones: Obtusilactones, Litsenolides, and Mahubanolides"]}]}],"canonical_facts":{"dc:creator":["Rollinson, Susan Lynn Wells"],"dc:date":["2014-12-13T20:11:06Z","10000-01-01","1980"],"dc:description":["Phenylselenenyl esters (methyl esters of 2-phenylselenenylhexadecanoic, 2-phenylselenenyloctadecanoic, and 2-phenylselenenyl-13-tetradecadienoic acids) were used as acrylate (alpha)-anion synthons in aldol addition reactions. The last acid above, bearing the terminal double bond, was synthesized by displacing the (omega)-bromide from methyl 11-bromo-2-phenylselenenylundecanoate by allyllithium. The other (alpha)-phenylselenenyl esters were made by quenching their lithium enolates with phenylselenenyl chloride. Addition to acrolein, followed by oxidation and selenoxide elimination gave the corresponding (alpha),(beta)-unsaturated esters bearing a 1-hydroxy-2-propenyl group at the (alpha)-carbon. Similarly, addition to propargylaldehyde followed by oxidative work-up gave the corresponding (alpha),(beta)-unsaturated esters bearing a 1-hydroxy-2-propynyl group at the (alpha)-carbon.","Hydrolysis of the olefinic esters to the corresponding carboxylic acids followed by lactonization (iodine or phenylselenenyl chloride) and hydrogenolysis (tri-n-butyltin hydride) gave (alpha)-alkylidene-(beta)-hydroxy-(gamma)-methyl-(gamma)-butyrolactones which are known natural products (litsenolides, dihydromahubanolides). Hydrolysis of the acetylenic esters to the corresponding carboxylic acids, followed by lactonization (mercuric trifluoroacetate or sodium bicarbonate) gave (alpha)-alkylidene-(beta)-hydroxy-(gamma)-methylene (gamma)-butyrolactones which are also known natural products (obtusilactones, mahubanolides). One of these, obtusilactone, the (gamma)-methylene lactone with the (alpha)-11-dodecenylidene moiety, has been reported to be cytotoxic.","Made available in DSpace on 2014-12-13T20:11:06Z (GMT). No. of bitstreams: 1 8108644.pdf: 3438344 bytes, checksum: d807d264c2b9b0059aa1476aa5e4aa10 (MD5) Previous issue date: 1980","Embargo set by: Seth Robbins for item 67428 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","126 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1980."],"dc:identifier":["http://hdl.handle.net/2142/67250","(UMI)AAI8108644"],"dc:language":["eng"],"dc:subject":["Chemistry, Organic"],"dc:title":["The Synthesis of Lauraceae Lactones: Obtusilactones, Litsenolides, and Mahubanolides"],"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":"2026-07-22T22:25:57Z"}