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Lewis base organocatalysts for carboxyl and acyl transfer reactions
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dc.contributor.advisor | Smith, Andrew David | |
dc.contributor.author | Woods, Philip A. | |
dc.coverage.spatial | 262 | en_US |
dc.date.accessioned | 2012-09-20T20:55:55Z | |
dc.date.available | 2012-09-20T20:55:55Z | |
dc.date.issued | 2011-08-15 | |
dc.identifier | uk.bl.ethos.556369 | |
dc.identifier.uri | https://hdl.handle.net/10023/3117 | |
dc.description.abstract | This thesis is concerned with the use of Lewis base organocatalysts for carboxyl and acyl transfer reactions. Chapter 1 introduces the ability of organic Lewis bases other than DMAP-type to promote a range of asymmetric O-, N- and C-acyl transfer processes. This chapter summarizes the developments in catalyst architectures and approaches to these processes that have been disclosed to date in this dynamic area of asymmetric organocatalysis. Chapter 2 introduces studies into the synthesis of pyrrolyl carbonates via cyclization of gamma-amino esters and ring closing metathesis (RCM) of N-allylamides. The ability of a range of Lewis bases to promote the regioselective O- to C-carboxyl transfer of pyrrolyl carbonates is also presented. Chapter 3 introduces isothiourea DHPB as an efficient Lewis base catalyst for the diastereoselective C-acylation of silyl ketene acetals with anhydrides or benzoyl fluoride, giving 3-acyl-3-aryl or 3-acyl-3-alkylfuranones in excellent yields and stereoselectivities (up to 99:1 dr). Chapter 4 introduces C(2)-aryl substituted DHPB derived-isothioureas as efficient Lewis base catalysts for the enantioselective C-acylation of silyl ketene acetals with propionic anhydride, giving 3-acyl-3-aryl or 3-acyl-3-alkylfuranones in good isolated yields and enantioselectivities (up to 98% ee). This chapter also demonstrates that these chiral isothioureas are required for high reactivity and asymmetry in related acylation manifolds. Chapter 5 presents and overall conclusion for chapters 2,3 and 4. Chapter 6 contains full experimental procedures and characterization data for all compounds synthesized in Chapters 2, 3 and 4. | en_US |
dc.language.iso | en | en_US |
dc.publisher | University of St Andrews | |
dc.subject | Asymmetric organocatalysis | en_US |
dc.subject | Lewis base catalysts | en_US |
dc.subject | Carboxyl and acyl transfer reactions | en_US |
dc.subject.lcc | QD262.W77 | |
dc.subject.lcsh | Asymmetric synthesis | en_US |
dc.subject.lcsh | Catalysts | en_US |
dc.subject.lcsh | Organic compounds--Synthesis | en_US |
dc.subject.lcsh | Lewis acids | en_US |
dc.title | Lewis base organocatalysts for carboxyl and acyl transfer reactions | 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.rights.embargodate | Print and electronic copy restricted until 14 November 2016 | en_US |
dc.rights.embargoreason | Electronic thesis unavailable: permission not provided to allow public access | en_US |
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