{"id":{"repo_id":"soton","oai_identifier":"oai:eprints.soton.ac.uk:71853"},"canonical_url":"https://search.dev.ndltd.org/etd/soton/oai:eprints.soton.ac.uk:71853","repository":{"repo_id":"soton","name":"University of Southampton","base_url":"https://eprints.soton.ac.uk/cgi/oai2"},"display":{"title":"CH activation and CH2 double activation of indolines: towards the synthesis of aspidospermidine and aspidofractinine","abstract":"This thesis is concerned with the total synthesis of the two Aspidosperma alkaloid natural products, aspidospermidine and aspidofractinine. The two targets have a common pentacyclic molecular framework unique to this class of indole alkaloids.<br/><br/>Aspidospermidine has previously proven an attractive target, with over 20 total syntheses completed. The hexacyclic framework of aspidofractinine has proven more challenging, with only 5 total syntheses to date. These synthetic approaches are discussed in Chapter 1 together with the pharmacological activity exhibited within the Aspidosperma alkaloid series.<br/><br/>Chapter 3 details the challenges of installing the first 4 rings of the targets (the ABDE ring system). Ring expansion of a C3 cyclopropyl indolone with an imine, ultimately provided a quick and efficient route to the tetracyclic structure. With the model system realised, Chapter 3 details the synthetic efforts towards an elaborated imine component and its subsequent use in the ring expansion methodology to give our key precursor.<br/><br/>Chapter 4 discusses model systems to prove our key radical translocation step can be achieved. Systems are described that show intramolecular translocation of an aryl radical to C2 of an indoline is a feasible means of elaborating this centre.","abstract_html":"This thesis is concerned with the total synthesis of the two Aspidosperma alkaloid natural products, aspidospermidine and aspidofractinine. The two targets have a common pentacyclic molecular framework unique to this class of indole alkaloids.&lt;br/&gt;&lt;br/&gt;Aspidospermidine has previously proven an attractive target, with over 20 total syntheses completed. The hexacyclic framework of aspidofractinine has proven more challenging, with only 5 total syntheses to date. These synthetic approaches are discussed in Chapter 1 together with the pharmacological activity exhibited within the Aspidosperma alkaloid series.&lt;br/&gt;&lt;br/&gt;Chapter 3 details the challenges of installing the first 4 rings of the targets (the ABDE ring system). Ring expansion of a C3 cyclopropyl indolone with an imine, ultimately provided a quick and efficient route to the tetracyclic structure. With the model system realised, Chapter 3 details the synthetic efforts towards an elaborated imine component and its subsequent use in the ring expansion methodology to give our key precursor.&lt;br/&gt;&lt;br/&gt;Chapter 4 discusses model systems to prove our key radical translocation step can be achieved. Systems are described that show intramolecular translocation of an aryl radical to C2 of an indoline is a feasible means of elaborating this centre.","abstract_has_math":false,"creators":["Whiting, Sally"],"institution":"University of Southampton","degree_name":"Ph.D.","degree_level":"doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Harrowven, David"],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-02","date_published":"2009-02","updated_at":"2026-07-24T04:36:06Z","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":["Harrowven, David"]},{"key":"dc:creator","label":"Author","values":["Whiting, Sally"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2009-02-15"]},{"key":"dc:date.issued","label":"Date","values":["2009-02"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Chemistry (pre 2011 reorg)","School of 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/71853/"]},{"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/71853/1/Full_thesis_inc_title_page_and_abstract.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This thesis is concerned with the total synthesis of the two Aspidosperma alkaloid natural products, aspidospermidine and aspidofractinine. The two targets have a common pentacyclic molecular framework unique to this class of indole alkaloids.<br/><br/>Aspidospermidine has previously proven an attractive target, with over 20 total syntheses completed. The hexacyclic framework of aspidofractinine has proven more challenging, with only 5 total syntheses to date. These synthetic approaches are discussed in Chapter 1 together with the pharmacological activity exhibited within the Aspidosperma alkaloid series.<br/><br/>Chapter 3 details the challenges of installing the first 4 rings of the targets (the ABDE ring system). Ring expansion of a C3 cyclopropyl indolone with an imine, ultimately provided a quick and efficient route to the tetracyclic structure. With the model system realised, Chapter 3 details the synthetic efforts towards an elaborated imine component and its subsequent use in the ring expansion methodology to give our key precursor.<br/><br/>Chapter 4 discusses model systems to prove our key radical translocation step can be achieved. Systems are described that show intramolecular translocation of an aryl radical to C2 of an indoline is a feasible means of elaborating this centre."]},{"key":"dc:format","label":"Dc Format","values":["text"]},{"key":"dc:title","label":"Title","values":["CH activation and CH2 double activation of indolines: towards the synthesis of aspidospermidine and aspidofractinine"]}]}],"canonical_facts":{"dc:contributor.advisor":["Harrowven, David"],"dc:creator":["Whiting, Sally"],"dc:date":["2009-02-15"],"dc:date.issued":["2009-02"],"dc:description.abstract":["This thesis is concerned with the total synthesis of the two Aspidosperma alkaloid natural products, aspidospermidine and aspidofractinine. The two targets have a common pentacyclic molecular framework unique to this class of indole alkaloids.<br/><br/>Aspidospermidine has previously proven an attractive target, with over 20 total syntheses completed. The hexacyclic framework of aspidofractinine has proven more challenging, with only 5 total syntheses to date. These synthetic approaches are discussed in Chapter 1 together with the pharmacological activity exhibited within the Aspidosperma alkaloid series.<br/><br/>Chapter 3 details the challenges of installing the first 4 rings of the targets (the ABDE ring system). Ring expansion of a C3 cyclopropyl indolone with an imine, ultimately provided a quick and efficient route to the tetracyclic structure. With the model system realised, Chapter 3 details the synthetic efforts towards an elaborated imine component and its subsequent use in the ring expansion methodology to give our key precursor.<br/><br/>Chapter 4 discusses model systems to prove our key radical translocation step can be achieved. Systems are described that show intramolecular translocation of an aryl radical to C2 of an indoline is a feasible means of elaborating this centre."],"dc:format":["text"],"dc:identifier.uri":["https://eprints.soton.ac.uk/71853/1/Full_thesis_inc_title_page_and_abstract.pdf"],"dc:publisher.department":["Chemistry (pre 2011 reorg)","School of Chemistry"],"dc:publisher.institution":["University of Southampton"],"dc:relation.isreferencedby":["https://eprints.soton.ac.uk/71853/"],"dc:title":["CH activation and CH2 double activation of indolines: towards the synthesis of aspidospermidine and aspidofractinine"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["doctoral"],"dc:type.qualificationname":["Ph.D."]},"updated_at":"2026-07-24T04:36:06Z"}