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Pyrrole acetic acid derivatives in Lewis base catalyzed enantioselective formal [4+2] cycloadditions
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dc.contributor.advisor | Smith, Andrew David | |
dc.contributor.author | Zhang, Shuyue | |
dc.coverage.spatial | [10], 293 p. | en_US |
dc.date.accessioned | 2020-06-12T14:21:15Z | |
dc.date.available | 2020-06-12T14:21:15Z | |
dc.date.issued | 2020-07-29 | |
dc.identifier.uri | https://hdl.handle.net/10023/20076 | |
dc.description.abstract | This thesis describes the use of C(1) ammonium enolate chemistry with Lewis base isothiourea catalysis in Michael addition-lactonization/lactamization between 2-pyrrolyl acetic acid derivatives and various Michael acceptors. Chapter 2 proved the principle that amino esters protected as benzophenone Schiff base could be α-functionalized using Lewis base catalysis. Chapter 3 described the use of 2-pyrrolyl acetic acid in enantioselective Michael addition-lactonization with CCl3 enone. After in situ ring-opening, a range of 30 diesters and diamides in up to 98% yield, >95:5 dr and >99:1 er. Further demonstration of the synthetic utility of these ring-opening derivatives was achieved with an intramolecular Friedel-Crafts acylation utilizing the electron-rich nature of pyrrole to afforded dihydroindolizinone derivatives in up to 90% yield with no erosion in stereoselectivity. Chapter 4 described the use of either α,β-unsaturated trifluoromethyl ketones or α-keto-β,γ-unsaturated esters with 2-pyrrolyl acetic acid to synthesize tetrahydroindolizine derivatives in one-pot, with up to 98% yield, >95:5 dr and >99:1 er. Chapter 5 described the synthesis of dihydropyridinones from chalcone-derived N-Ts ketimine and unsaturated cyclic sulfonamide derived from saccharin in up to 97% yield, >95:5 dr and >99:1 er. Chapter 6 described the synthesis of tetrasubstituted pyridines using a variety of unsaturated ketimines bearing esters with DHPB catalyst in up to 66% yield. Further derivatization was demonstrated via transforming 2-pivaloyloxy group into 2-OTs group in a two-step process, enabling the Pd-catalyzed cross coupling and reduction. | en_US |
dc.language.iso | en | en_US |
dc.publisher | University of St Andrews | |
dc.rights | Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.subject | Lewis base | en_US |
dc.subject | Isothiourea catalysis | en_US |
dc.subject | Michael addition | en_US |
dc.subject | Pyrrolyl acetic acid | en_US |
dc.subject | Enantioselective synthesis | en_US |
dc.subject.lcc | QD505.Z5 | |
dc.subject.lcsh | Enantioselective catalysis | en |
dc.subject.lcsh | Catalysis | en |
dc.subject.lcsh | Pyrroles--Derivatives | en |
dc.subject.lcsh | Thiourea | en |
dc.title | Pyrrole acetic acid derivatives in Lewis base catalyzed enantioselective formal [4+2] cycloadditions | en_US |
dc.type | Thesis | en_US |
dc.type.qualificationlevel | Doctoral | en_US |
dc.type.qualificationname | PhD Doctor of Philosophy | en_US |
dc.publisher.institution | The University of St Andrews | en_US |
dc.identifier.doi | https://doi.org/10.17630/10023-20076 |
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