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dc.contributor.authorLaBine, Emily
dc.contributor.otherQueen's University (Kingston, Ont.). Theses (Queen's University (Kingston, Ont.))en
dc.date2013-11-12 19:05:19.488en
dc.date.accessioned2013-11-14T18:40:02Z
dc.date.available2013-11-14T18:40:02Z
dc.date.issued2013-11-14
dc.identifier.urihttp://hdl.handle.net/1974/8463
dc.descriptionThesis (Master, Chemistry) -- Queen's University, 2013-11-12 19:05:19.488en
dc.description.abstractThe stereochemical course of the Pd–catalyzed Suzuki-Miyaura cross-coupling of α-substituted, enantioenriched allylic boronic esters with phenyl iodide has been examined. The secondary boronic esters were prepared in both racemic and enantioenriched forms via borylationof a lithiated carbenoid with a geometrically defined vinyl boronic ester. The geometric purities were determined to be >99% and the enantiomeric excesses of stereodefined secondary boronic esters were found to exceed 98:2. In total, 8 allylic boronic esters were successfully cross-coupled, providing arylated products with high regioselectivities (>90:10) and complete enantiospecificities (>99%). The cross-coupling of a sterically and electronically unbiased, deuterated substrate confirmed that fully equilibrated π-allylic intermediates are not involved. Additionally, correlating the absolute configurations of the allylic boronic ester and the cross-coupling product allowed us to confirm that the transmetalation step of the reaction proceeded through a closed transition state via a syn-SE’ mechanism, which further suggests the importance of the distinct Pd-O-B bond linkage. Further, the cross-coupling of vinyl iodides to secondary boronic esters was investigated.en_US
dc.languageenen
dc.language.isoenen_US
dc.relation.ispartofseriesCanadian thesesen
dc.rightsThis publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner.en
dc.subjectSuzuki-Miyauraen_US
dc.subjectRegioselectiveen_US
dc.subjectCatalysisen_US
dc.subjectEnantiospecificen_US
dc.subjectCross-Couplingen_US
dc.titleEnantiospecific, Regioselective Suzuki-Miyaura Cross-Couplings of Secondary, Allylic Boronic Estersen_US
dc.typeThesisen_US
dc.description.degreeMasteren
dc.contributor.supervisorCrudden, Cathleen M.en
dc.contributor.departmentChemistryen


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