{"id":{"repo_id":"soton","oai_identifier":"oai:eprints.soton.ac.uk:209775"},"canonical_url":"https://search.dev.ndltd.org/etd/soton/oai:eprints.soton.ac.uk:209775","repository":{"repo_id":"soton","name":"University of Southampton","base_url":"https://eprints.soton.ac.uk/cgi/oai2"},"display":{"title":"Synthesis of furanosesquiterpenoid natural products","abstract":"The effect of addition of a catalytic quantity of a crown ether in the reaction of a phosphonate anion with a carbonyl compound (Wadsworth-Emmons reaction) has been studied and found to greatly facilitate this reaction. This modification of the Wadsworth-Emmons reaction, using a catalytic amount of 15-crown-5, has been employed in the synthesis of the naturally occurring furanosesquiterpene Pallescensin-E. The structure of this compound has been confirmed by comparison of its spectral data with that of the synthesised isomer, 4,l0-dihydro-7,8-dimethyl 10H-benzof4,5Jcycloheptafl,2-bJ furan.<br/><br/>Homosesquirosefuran, an analogue of the naturally occurring furanosesquiterpene Sesquirosefuran, has been synthesised via the dianion of methylacetoacetate.<br/><br/>An approach to the synthesis of Pinguisone (a component of the essential oil of the liverwort Aneura pinguis)has been attempted employing two Diels-Alder reactions to generate the four cis-methyl groups found in the natural product.<br/><br/>In a study of the reaction of n-(2-methylallyl)nickel bromide complex with a range of epoxides, this complex was found not only to react with reactive epoxides (e.g. styrene epoxide) but also with less reactive propylene epoxide.<br/><br/>Substrates for possible intramolecular n-allylnickel cyclisation to generate an a-methylene-6-valerolactone ring system have been prepared.","abstract_html":"The effect of addition of a catalytic quantity of a crown ether in the reaction of a phosphonate anion with a carbonyl compound (Wadsworth-Emmons reaction) has been studied and found to greatly facilitate this reaction. This modification of the Wadsworth-Emmons reaction, using a catalytic amount of 15-crown-5, has been employed in the synthesis of the naturally occurring furanosesquiterpene Pallescensin-E. The structure of this compound has been confirmed by comparison of its spectral data with that of the synthesised isomer, 4,l0-dihydro-7,8-dimethyl 10H-benzof4,5Jcycloheptafl,2-bJ furan.&lt;br/&gt;&lt;br/&gt;Homosesquirosefuran, an analogue of the naturally occurring furanosesquiterpene Sesquirosefuran, has been synthesised via the dianion of methylacetoacetate.&lt;br/&gt;&lt;br/&gt;An approach to the synthesis of Pinguisone (a component of the essential oil of the liverwort Aneura pinguis)has been attempted employing two Diels-Alder reactions to generate the four cis-methyl groups found in the natural product.&lt;br/&gt;&lt;br/&gt;In a study of the reaction of n-(2-methylallyl)nickel bromide complex with a range of epoxides, this complex was found not only to react with reactive epoxides (e.g. styrene epoxide) but also with less reactive propylene epoxide.&lt;br/&gt;&lt;br/&gt;Substrates for possible intramolecular n-allylnickel cyclisation to generate an a-methylene-6-valerolactone ring system have been prepared.","abstract_has_math":false,"creators":["Sims, Russell John"],"institution":"University of Southampton","degree_name":"Ph.D.","degree_level":"doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Baker, Ray"],"committee_chairs":[],"committee_members":[],"year":1981,"date_issued":"1981-10","date_published":"1981-10","updated_at":"2026-07-24T04:36:36Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Baker, Ray"]},{"key":"dc:creator","label":"Author","values":["Sims, Russell John"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["1981-10"]},{"key":"dc:date.issued","label":"Date","values":["1981-10"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Faculty of Natural and Environmental Sciences (pre 2018 reorg)","Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Southampton"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://eprints.soton.ac.uk/209775/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["Ph.D."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://eprints.soton.ac.uk/209775/1/82010126.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The effect of addition of a catalytic quantity of a crown ether in the reaction of a phosphonate anion with a carbonyl compound (Wadsworth-Emmons reaction) has been studied and found to greatly facilitate this reaction. This modification of the Wadsworth-Emmons reaction, using a catalytic amount of 15-crown-5, has been employed in the synthesis of the naturally occurring furanosesquiterpene Pallescensin-E. The structure of this compound has been confirmed by comparison of its spectral data with that of the synthesised isomer, 4,l0-dihydro-7,8-dimethyl 10H-benzof4,5Jcycloheptafl,2-bJ furan.<br/><br/>Homosesquirosefuran, an analogue of the naturally occurring furanosesquiterpene Sesquirosefuran, has been synthesised via the dianion of methylacetoacetate.<br/><br/>An approach to the synthesis of Pinguisone (a component of the essential oil of the liverwort Aneura pinguis)has been attempted employing two Diels-Alder reactions to generate the four cis-methyl groups found in the natural product.<br/><br/>In a study of the reaction of n-(2-methylallyl)nickel bromide complex with a range of epoxides, this complex was found not only to react with reactive epoxides (e.g. styrene epoxide) but also with less reactive propylene epoxide.<br/><br/>Substrates for possible intramolecular n-allylnickel cyclisation to generate an a-methylene-6-valerolactone ring system have been prepared."]},{"key":"dc:format","label":"Dc Format","values":["text"]},{"key":"dc:title","label":"Title","values":["Synthesis of furanosesquiterpenoid natural products"]}]}],"canonical_facts":{"dc:contributor.advisor":["Baker, Ray"],"dc:creator":["Sims, Russell John"],"dc:date":["1981-10"],"dc:date.issued":["1981-10"],"dc:description.abstract":["The effect of addition of a catalytic quantity of a crown ether in the reaction of a phosphonate anion with a carbonyl compound (Wadsworth-Emmons reaction) has been studied and found to greatly facilitate this reaction. This modification of the Wadsworth-Emmons reaction, using a catalytic amount of 15-crown-5, has been employed in the synthesis of the naturally occurring furanosesquiterpene Pallescensin-E. The structure of this compound has been confirmed by comparison of its spectral data with that of the synthesised isomer, 4,l0-dihydro-7,8-dimethyl 10H-benzof4,5Jcycloheptafl,2-bJ furan.<br/><br/>Homosesquirosefuran, an analogue of the naturally occurring furanosesquiterpene Sesquirosefuran, has been synthesised via the dianion of methylacetoacetate.<br/><br/>An approach to the synthesis of Pinguisone (a component of the essential oil of the liverwort Aneura pinguis)has been attempted employing two Diels-Alder reactions to generate the four cis-methyl groups found in the natural product.<br/><br/>In a study of the reaction of n-(2-methylallyl)nickel bromide complex with a range of epoxides, this complex was found not only to react with reactive epoxides (e.g. styrene epoxide) but also with less reactive propylene epoxide.<br/><br/>Substrates for possible intramolecular n-allylnickel cyclisation to generate an a-methylene-6-valerolactone ring system have been prepared."],"dc:format":["text"],"dc:identifier.uri":["https://eprints.soton.ac.uk/209775/1/82010126.pdf"],"dc:publisher.department":["Faculty of Natural and Environmental Sciences (pre 2018 reorg)","Chemistry"],"dc:publisher.institution":["University of Southampton"],"dc:relation.isreferencedby":["https://eprints.soton.ac.uk/209775/"],"dc:title":["Synthesis of furanosesquiterpenoid natural products"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["doctoral"],"dc:type.qualificationname":["Ph.D."]},"updated_at":"2026-07-24T04:36:36Z"}