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dc.contributor.authorSenge, Mathias
dc.contributor.authorKielmann, Marc
dc.contributor.authorGrover, Nitika
dc.contributor.authorKalisch, Werner W.
dc.date.accessioned2020-02-04T17:04:59Z
dc.date.available2020-02-04T17:04:59Z
dc.date.issued2019
dc.date.submitted2019en
dc.identifier.citationKielmann, M., Grover, N., Kalisch, W.W. & Senge, M.O., Incremental Introduction of Organocatalytic Activity into Conformationally Engineered Porphyrins, 2019, European Journal of Organic Chemistry, 2019, 14en
dc.identifier.otherY
dc.identifier.urihttps://onlinelibrary.wiley.com/doi/full/10.1002/ejoc.201801691
dc.identifier.urihttp://hdl.handle.net/2262/91441
dc.description.abstractTo study the correlation of macrocycle nonplanarity and catalytic activity of free base porphyrins in detail, a series of six tetraphenylporphyrins with graded degree of β‐ethyl substitution (“H2EtxTPPs” 1–6; x = 0, 2, 4, 6, 8) was applied in organocatalyzed reactions. The macrocycles display incrementally increasing nonplanarity due to repulsive peri‐interactions. This creates an out‐of‐plane vector and better accessibility of the core amine and imine groups as the number of alkyl substituents increases. Following such a molecular engineering approach, the inner core system could be used to activate small molecules as a result of significant saddle distortion. The potential organocatalyst “H2EtxTPPs” were used in benchmark sulfa‐Michael reactions and we found a distinct relationship between nonplanarity and conversion. These observations were attributed to the combined effect of enhanced basicity and increased H‐bonding potential that could facilitate bifunctional organocatalysis. Ultimately, density functional theory (DFT) calculations were performed on 1–6 to monitor some electronic properties of the title compounds.en
dc.format.extent2448-2452en
dc.language.isoenen
dc.relation.ispartofseriesEuropean Journal of Organic Chemistry;
dc.relation.ispartofseries2019;
dc.relation.ispartofseries14;
dc.rightsYen
dc.subjectHydrogen bondsen
dc.subjectMacrocyclesen
dc.subjectMolecular engineeringen
dc.subjectOrganocatalysisen
dc.subjectPorphyrinsen
dc.titleIncremental Introduction of Organocatalytic Activity into Conformationally Engineered Porphyrinsen
dc.typeJournal Articleen
dc.contributor.sponsorScience Foundation Irelanden
dc.type.supercollectionscholarly_publicationsen
dc.type.supercollectionrefereed_publicationsen
dc.identifier.peoplefinderurlhttp://people.tcd.ie/sengem
dc.identifier.rssinternalid206057
dc.identifier.doihttp://dx.doi.org/10.1002/ejoc.201801691
dc.rights.ecaccessrightsopenAccess
dc.contributor.sponsorGrantNumberSFI IvP 13/IA/1894en


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