dc.contributor.author | White, Kolby L. | |
dc.contributor.author | Mewald, Marius | |
dc.contributor.author | Movassaghi, Mohammad | |
dc.date.accessioned | 2017-06-26T19:56:57Z | |
dc.date.available | 2017-06-26T19:56:57Z | |
dc.date.issued | 2015-07 | |
dc.identifier.issn | 0022-3263 | |
dc.identifier.issn | 1520-6904 | |
dc.identifier.uri | http://hdl.handle.net/1721.1/110277 | |
dc.description.abstract | The first mechanistic investigation of electrophilic amide activation of α,α-disubstituted tertiary lactams and the direct observation of key intermediates by in situ FTIR, 1H, 13C, and 19F NMR in our interrupted Bischler–Napieralski-based synthetic strategy to the aspidosperma alkaloids, including a complex tetracyclic diiminium ion, is discussed. The reactivity of a wide range of pyridines with trifluoromethanesulfonic anhydride was systematically examined, and characteristic IR absorption bands for the corresponding N-trifluoromethanesulfonylated pyridinium trifluoromethanesulfonates were assigned. The reversible formation of diiminium ether intermediates was studied, providing insight into divergent mechanistic pathways as a function of the steric environment of the amide substrate and stoichiometry of reagents. Importantly, when considering base additives during electrophilic amide activation, more hindered α-quaternary tertiary lactams require the use of non-nucleophilic pyridine additives in order to avoid deactivation via a competing desulfonylation reaction. The isolation and full characterization of a tetracyclic iminium trifluoromethanesulfonate provided additional correlation between in situ characterization of sensitive intermediates and isolable compounds involved in this synthetic transformation. | en_US |
dc.description.sponsorship | National Institute of General Medical Sciences (U.S.) (GM074825) | en_US |
dc.description.sponsorship | National Science Foundation (U.S.). Graduate Research Fellowship Program | en_US |
dc.description.sponsorship | German Academic Exchange Service | en_US |
dc.language.iso | en_US | |
dc.publisher | American Chemical Society (ACS) | en_US |
dc.relation.isversionof | http://dx.doi.org/10.1021/acs.joc.5b01023 | en_US |
dc.rights | Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. | en_US |
dc.source | PMC | en_US |
dc.title | Direct Observation of Intermediates Involved in the Interruption of the Bischler–Napieralski Reaction | en_US |
dc.type | Article | en_US |
dc.identifier.citation | White, Kolby L., Marius Mewald, and Mohammad Movassaghi. “Direct Observation of Intermediates Involved in the Interruption of the Bischler?Napieralski Reaction.” The Journal of Organic Chemistry 80.15 (2015): 7403–7411. | en_US |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemistry | en_US |
dc.contributor.mitauthor | White, Kolby L. | |
dc.contributor.mitauthor | Mewald, Marius | |
dc.contributor.mitauthor | Movassaghi, Mohammad | |
dc.relation.journal | Journal of Organic Chemistry | en_US |
dc.eprint.version | Author's final manuscript | en_US |
dc.type.uri | http://purl.org/eprint/type/JournalArticle | en_US |
eprint.status | http://purl.org/eprint/status/PeerReviewed | en_US |
dspace.orderedauthors | White, Kolby L.; Mewald, Marius; Movassaghi, Mohammad | en_US |
dspace.embargo.terms | N | en_US |
dc.identifier.orcid | https://orcid.org/0000-0003-3080-1063 | |
mit.license | PUBLISHER_POLICY | en_US |
mit.metadata.status | Complete | |