{"id":{"repo_id":"soton","oai_identifier":"oai:eprints.soton.ac.uk:187747"},"canonical_url":"https://search.dev.ndltd.org/etd/soton/oai:eprints.soton.ac.uk:187747","repository":{"repo_id":"soton","name":"University of Southampton","base_url":"https://eprints.soton.ac.uk/cgi/oai2"},"display":{"title":"A new cyclohexyl-based chiral auxiliary: application in the total synthesis of (+)-linalool oxide","abstract":"Seven different racemic cyclohexyl-based chiral auxiliaries (2.4-2.10) were synthesised in moderate to good yields (38-85%) by nucleophilic opening of cyclohexene oxide using carbanions. The racemic cyclohexyl-based chiral auxiliaries were coupled with the 6-methyl-2- methylenehept-5-enoyl chloride (2.20) to form the dienes esters 2.38-2.44. The chiral auxiliarydiene ester adducts 2.38-2.44 were subjected to a comparative study in the permanganatemediated oxidative cyclisation. The best result was obtained by using (±)-trans-2-trityl-1- cyclohexanol ((±)-2.10 (±)-TTC)), resulting in high diastereoselectivity (dr = 97:3) in the resulting THF diols 2.51a/b. The other auxiliaries synthesised gave only moderate to no diastereoinduction. Different methods were used to resolve the racemic auxiliary (±)-TTC including enzymatic resolution and classical resolution. A successful classical resolution was achieved and the enantiomer (–)-TTC was obtained in excellent yield and enantiopurity (99 % ee). The stereochemistry of the obtained enantiomer was defined as (1S,2R) from the X-ray structure of its Mosher ester derivative 2.76. (–)-TTC was used in the total synthesis of (+)-linalool oxide (1.247) which was achieved in 9 steps and 13% overall yield. Finally, nucleophilic additions to ?-keto esters containing (±)-TTC were investigated and the preliminary results are described","abstract_html":"Seven different racemic cyclohexyl-based chiral auxiliaries (2.4-2.10) were synthesised in moderate to good yields (38-85%) by nucleophilic opening of cyclohexene oxide using carbanions. The racemic cyclohexyl-based chiral auxiliaries were coupled with the 6-methyl-2- methylenehept-5-enoyl chloride (2.20) to form the dienes esters 2.38-2.44. The chiral auxiliarydiene ester adducts 2.38-2.44 were subjected to a comparative study in the permanganatemediated oxidative cyclisation. The best result was obtained by using (±)-trans-2-trityl-1- cyclohexanol ((±)-2.10 (±)-TTC)), resulting in high diastereoselectivity (dr = 97:3) in the resulting THF diols 2.51a/b. The other auxiliaries synthesised gave only moderate to no diastereoinduction. Different methods were used to resolve the racemic auxiliary (±)-TTC including enzymatic resolution and classical resolution. A successful classical resolution was achieved and the enantiomer (–)-TTC was obtained in excellent yield and enantiopurity (99 % ee). The stereochemistry of the obtained enantiomer was defined as (1S,2R) from the X-ray structure of its Mosher ester derivative 2.76. (–)-TTC was used in the total synthesis of (+)-linalool oxide (1.247) which was achieved in 9 steps and 13% overall yield. Finally, nucleophilic additions to ?-keto esters containing (±)-TTC were investigated and the preliminary results are described","abstract_has_math":false,"creators":["Al-Hazmi, Ali"],"institution":"University of Southampton","degree_name":"Ph.D.","degree_level":"doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Brown, Richard C.D."],"committee_chairs":[],"committee_members":[],"year":2010,"date_issued":"2010-06","date_published":"2010-06","updated_at":"2026-07-24T04:36:25Z","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":["Brown, Richard C.D."]},{"key":"dc:creator","label":"Author","values":["Al-Hazmi, Ali"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2010-06-01"]},{"key":"dc:date.issued","label":"Date","values":["2010-06"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Chemistry (pre 2011 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/187747/"]},{"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/187747/1/thesis_electronic_version_A._M._Al_Hazmi_.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Seven different racemic cyclohexyl-based chiral auxiliaries (2.4-2.10) were synthesised in moderate to good yields (38-85%) by nucleophilic opening of cyclohexene oxide using carbanions. The racemic cyclohexyl-based chiral auxiliaries were coupled with the 6-methyl-2- methylenehept-5-enoyl chloride (2.20) to form the dienes esters 2.38-2.44. The chiral auxiliarydiene ester adducts 2.38-2.44 were subjected to a comparative study in the permanganatemediated oxidative cyclisation. The best result was obtained by using (±)-trans-2-trityl-1- cyclohexanol ((±)-2.10 (±)-TTC)), resulting in high diastereoselectivity (dr = 97:3) in the resulting THF diols 2.51a/b. The other auxiliaries synthesised gave only moderate to no diastereoinduction. Different methods were used to resolve the racemic auxiliary (±)-TTC including enzymatic resolution and classical resolution. A successful classical resolution was achieved and the enantiomer (–)-TTC was obtained in excellent yield and enantiopurity (99 % ee). The stereochemistry of the obtained enantiomer was defined as (1S,2R) from the X-ray structure of its Mosher ester derivative 2.76. (–)-TTC was used in the total synthesis of (+)-linalool oxide (1.247) which was achieved in 9 steps and 13% overall yield. Finally, nucleophilic additions to ?-keto esters containing (±)-TTC were investigated and the preliminary results are described"]},{"key":"dc:format","label":"Dc Format","values":["text"]},{"key":"dc:title","label":"Title","values":["A new cyclohexyl-based chiral auxiliary: application in the total synthesis of (+)-linalool oxide"]}]}],"canonical_facts":{"dc:contributor.advisor":["Brown, Richard C.D."],"dc:creator":["Al-Hazmi, Ali"],"dc:date":["2010-06-01"],"dc:date.issued":["2010-06"],"dc:description.abstract":["Seven different racemic cyclohexyl-based chiral auxiliaries (2.4-2.10) were synthesised in moderate to good yields (38-85%) by nucleophilic opening of cyclohexene oxide using carbanions. The racemic cyclohexyl-based chiral auxiliaries were coupled with the 6-methyl-2- methylenehept-5-enoyl chloride (2.20) to form the dienes esters 2.38-2.44. The chiral auxiliarydiene ester adducts 2.38-2.44 were subjected to a comparative study in the permanganatemediated oxidative cyclisation. The best result was obtained by using (±)-trans-2-trityl-1- cyclohexanol ((±)-2.10 (±)-TTC)), resulting in high diastereoselectivity (dr = 97:3) in the resulting THF diols 2.51a/b. The other auxiliaries synthesised gave only moderate to no diastereoinduction. Different methods were used to resolve the racemic auxiliary (±)-TTC including enzymatic resolution and classical resolution. A successful classical resolution was achieved and the enantiomer (–)-TTC was obtained in excellent yield and enantiopurity (99 % ee). The stereochemistry of the obtained enantiomer was defined as (1S,2R) from the X-ray structure of its Mosher ester derivative 2.76. (–)-TTC was used in the total synthesis of (+)-linalool oxide (1.247) which was achieved in 9 steps and 13% overall yield. Finally, nucleophilic additions to ?-keto esters containing (±)-TTC were investigated and the preliminary results are described"],"dc:format":["text"],"dc:identifier.uri":["https://eprints.soton.ac.uk/187747/1/thesis_electronic_version_A._M._Al_Hazmi_.pdf"],"dc:publisher.department":["Chemistry (pre 2011 reorg)","Chemistry"],"dc:publisher.institution":["University of Southampton"],"dc:relation.isreferencedby":["https://eprints.soton.ac.uk/187747/"],"dc:title":["A new cyclohexyl-based chiral auxiliary: application in the total synthesis of (+)-linalool oxide"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["doctoral"],"dc:type.qualificationname":["Ph.D."]},"updated_at":"2026-07-24T04:36:25Z"}