Vinylogous Mukaiyama aldol reactions with 4-oxy-2-trimethylsilyloxypyrroles: relevance to castanospermine synthesis

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dc.contributor.authorHunter, Rogeren_ZA
dc.contributor.authorRees-Jones, Sophieen_ZA
dc.contributor.authorSu, Hongen_ZA
dc.date.accessioned2015-10-12T11:03:21Z
dc.date.available2015-10-12T11:03:21Z
dc.date.issued2007en_ZA
dc.description.abstractBACKGROUND:The diastereoselectivity of a vinylogous Mukaiyama aldol reaction of a series of N-substituted 4-oxy-2-trimethylsilyloxypyrroles with a tartrate-based aldehyde has been explored as a model reaction for castanospermine synthesis. RESULTS: The study has revealed that the reaction is sensitive to the nature of the combination of N- and 4-oxy substituents. With a N-PMB or N-Bn and 4-methoxy combination, the reaction generates an aldol adduct with the correct absolute configurations for C-8 and C-8a of the indolizidine alkaloid castanospermine. The adduct was transformed to an indolizidine, whose ketal could not be transformed appropriately for the target alkaloid. CONCLUSION: The first successful diastereoselective Mukaiyama aldol strategy for the C-8 and C-8a stereogenic centres of castanospermine is presented using silyloxypyrrole chemistry. The results suggest that a full enantioselective synthesis can be realized provided that C-1 functionalisation is accomplished early in the synthesis, post-coupling.en_ZA
dc.identifier.apacitationHunter, R., Rees-Jones, S., & Su, H. (2007). Vinylogous Mukaiyama aldol reactions with 4-oxy-2-trimethylsilyloxypyrroles: relevance to castanospermine synthesis. <i>Beilstein Journal of Organic Chemistry</i>, http://hdl.handle.net/11427/14222en_ZA
dc.identifier.chicagocitationHunter, Roger, Sophie Rees-Jones, and Hong Su "Vinylogous Mukaiyama aldol reactions with 4-oxy-2-trimethylsilyloxypyrroles: relevance to castanospermine synthesis." <i>Beilstein Journal of Organic Chemistry</i> (2007) http://hdl.handle.net/11427/14222en_ZA
dc.identifier.citationHunter, R., Rees-Jones, S. C., & Su, H. (2007). Vinylogous Mukaiyama aldol reactions with 4-oxy-2-trimethylsilyloxypyrroles: relevance to castanospermine synthesis. Beilstein journal of organic chemistry, 3(1), 38.en_ZA
dc.identifier.ris TY - Journal Article AU - Hunter, Roger AU - Rees-Jones, Sophie AU - Su, Hong AB - BACKGROUND:The diastereoselectivity of a vinylogous Mukaiyama aldol reaction of a series of N-substituted 4-oxy-2-trimethylsilyloxypyrroles with a tartrate-based aldehyde has been explored as a model reaction for castanospermine synthesis. RESULTS: The study has revealed that the reaction is sensitive to the nature of the combination of N- and 4-oxy substituents. With a N-PMB or N-Bn and 4-methoxy combination, the reaction generates an aldol adduct with the correct absolute configurations for C-8 and C-8a of the indolizidine alkaloid castanospermine. The adduct was transformed to an indolizidine, whose ketal could not be transformed appropriately for the target alkaloid. CONCLUSION: The first successful diastereoselective Mukaiyama aldol strategy for the C-8 and C-8a stereogenic centres of castanospermine is presented using silyloxypyrrole chemistry. The results suggest that a full enantioselective synthesis can be realized provided that C-1 functionalisation is accomplished early in the synthesis, post-coupling. DA - 2007 DB - OpenUCT DO - 10.1186/1860-5397-3-38 DP - University of Cape Town J1 - Beilstein Journal of Organic Chemistry LK - https://open.uct.ac.za PB - University of Cape Town PY - 2007 T1 - Vinylogous Mukaiyama aldol reactions with 4-oxy-2-trimethylsilyloxypyrroles: relevance to castanospermine synthesis TI - Vinylogous Mukaiyama aldol reactions with 4-oxy-2-trimethylsilyloxypyrroles: relevance to castanospermine synthesis UR - http://hdl.handle.net/11427/14222 ER - en_ZA
dc.identifier.urihttp://hdl.handle.net/11427/14222
dc.identifier.urihttp://dx.doi.org/10.1186/1860-5397-3-38
dc.identifier.vancouvercitationHunter R, Rees-Jones S, Su H. Vinylogous Mukaiyama aldol reactions with 4-oxy-2-trimethylsilyloxypyrroles: relevance to castanospermine synthesis. Beilstein Journal of Organic Chemistry. 2007; http://hdl.handle.net/11427/14222.en_ZA
dc.language.isoengen_ZA
dc.publisherBiomed Centralen_ZA
dc.publisher.departmentDepartment of Chemistryen_ZA
dc.publisher.facultyFaculty of Scienceen_ZA
dc.publisher.institutionUniversity of Cape Town
dc.rightsThis is an Open Access article distributed under the terms of the Creative Commons Attribution Licenseen_ZA
dc.rights.urihttp://creativecommons.org/licenses/by/2.0en_ZA
dc.sourceBeilstein Journal of Organic Chemistryen_ZA
dc.source.urihttp://www.biomedcentral.com/1860-5397/en_ZA
dc.subject.otherIndolizidines and quinolizidinesen_ZA
dc.titleVinylogous Mukaiyama aldol reactions with 4-oxy-2-trimethylsilyloxypyrroles: relevance to castanospermine synthesisen_ZA
dc.typeJournal Articleen_ZA
uct.type.filetypeText
uct.type.filetypeImage
uct.type.publicationResearchen_ZA
uct.type.resourceArticleen_ZA
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