Predicting the Outcome of Photocyclisation Reactions: A Joint Experimental and Computational Investigation

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dc.contributor.authorFitchett, Christopher
dc.contributor.authorCrittenden, Deborah
dc.contributor.authorWonanke, Dinga
dc.contributor.authorFerguson, Jayne Louise
dc.date.accessioned2023-03-15T01:46:39Z
dc.date.available2023-03-15T01:46:39Z
dc.date.issued2019en
dc.date.updated2023-02-13T02:02:26Z
dc.description.abstractPhotochemical oxidative cyclodehydrogenation reactions are a versatile class of aromatic ring-forming reactions. They are tolerant to functional group substitution and heteroatom inclusion, so can be used to form a diverse range of extended polyaromatic systems by fusing existing ring substituents. However, despite their undoubted synthetic utility, there are no existing models—computational or heuristic—that predict the outcome of photocyclisation reactions across all possible classes of reactants. This can be traced back to the fact that “negative” results are rarely published in the synthetic literature and the lack of a general conceptual framework for understanding how photoexcitation affects reactivity. In this work, we address both of these issues. We present experimental data for a series of aromatically substituted pyrroles and indoles, and show that quantifying induced atomic forces upon photoexcitation provides a powerful predictive model for determining whether a given reactant will photoplanarise and hence proceed to photocyclised product under appropriate reaction conditions. The propensity of a molecule to photoplanarise is related to localised changes in charge distribution around the putative forming ring upon photoexcitation. This is promoted by asymmetry in molecular structures and/or charge distributions, inclusion of heteroatoms and ethylene bridging and well-separated or isolated photocyclisation sites.en
dc.identifier.citationWonanke ADD, Ferguson JL, Fitchett CM, Crittenden DL (2019). Predicting the Outcome of Photocyclisation Reactions: A Joint Experimental and Computational Investigation. Chemistry - An Asian Journal. 14(8). 1293-1303.en
dc.identifier.doihttp://doi.org/10.1002/asia.201801761
dc.identifier.issn1861-4728
dc.identifier.issn1861-471X
dc.identifier.urihttps://hdl.handle.net/10092/105229
dc.languageeng
dc.language.isoenen
dc.publisherWileyen
dc.rightsAll rights reserved unless otherwise stateden
dc.rights.urihttp://hdl.handle.net/10092/17651en
dc.subjectab initio calculationsen
dc.subjectphotocyclizationen
dc.subjectphotoplanarizationen
dc.subjectoxidative cyclodehydrogenationen
dc.subjectreactivity predictoren
dc.subject.anzsrc03 Chemical Sciencesen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3405 - Organic chemistry::340503 - Organic chemical synthesisen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3406 - Physical chemistry::340606 - Photochemistryen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3406 - Physical chemistry::340607 - Reaction kinetics and dynamicsen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3405 - Organic chemistry::340505 - Physical organic chemistry
dc.titlePredicting the Outcome of Photocyclisation Reactions: A Joint Experimental and Computational Investigationen
dc.typeJournal Articleen
uc.collegeFaculty of Science
uc.departmentSchool of Physical & Chemical Sciences
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