Noncovalent Modulation of Chemoselectivity in the Gas Phase Leads to a Switchover in Reaction Type from Heterolytic to Homolytic to Electrocyclic Cleavage
Nau, W. M., Moorthy, S., Lambert, H., Mohan, N., Schwarzlose, T., Kalenius, E., & Lee, T.-C. (2023). Noncovalent Modulation of Chemoselectivity in the Gas Phase Leads to a Switchover in Reaction Type from Heterolytic to Homolytic to Electrocyclic Cleavage. Angewandte Chemie, 62(32), Article e202303491. https://doi.org/10.1002/anie.202303491
Julkaistu sarjassa
Angewandte ChemieTekijät
Päivämäärä
2023Oppiaine
Analyyttinen kemiaNanoscience CenterOrgaaninen kemiaAnalytical ChemistryNanoscience CenterOrganic ChemistryTekijänoikeudet
© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
In the gas phase, thermal activation of supramolecular assemblies such as host-guest complexes leads commonly to noncovalent dissociation into the individual components. Chemical reactions, for example of encapsulated guest molecules, are only found in exceptional cases. As observed by mass spectrometry, when 1-amino-methyl-2,3-diazabicyclo[2.2.2]oct-2-ene (DBOA) is complexed by the macrocycle b-cyclodextrin, its protonated complex undergoes collision-induced dissociation into its components, the conventional reaction pathway. Inside the macrocyclic cavity of cucurbit[7]uril (CB7), a competitive chemical reaction of monoprotonated DBOA takes place upon thermal activation, namely a stepwise homolytic covalent bond cleavage with the elimination of N2, while the doubly protonated CB7•DBOA complex undergoes an inner-phase elimination of ethylene, a concerted, electrocyclic ring-opening reaction. These chemical reaction pathways stand in contrast to the gas-phase chemistry of uncomplexed monoprotonated DBOA, for which an elimination of NH3 predominates upon collision-induced activation, as a heterolytic bond cleavage reaction. The combined results, which can be rationalized in terms of organic-chemical reaction mechanisms and density-function theoretical calculations, demonstrate that chemical reactions in the gas phase can be steered chemoselectively through noncovalent interactions.
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1433-7851Asiasanat
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https://converis.jyu.fi/converis/portal/detail/Publication/183167880
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SM, NM, EK, and TCL are grateful to the Research Project Grant (RPG-2016-393) funded by the Leverhulme Trust. HL and TCL are grateful to the Studentship funded by the A*STAR-UCL Research Attachment Programme through the EPSRC M3S CDT (EP/L015862/1). The authors acknowledge the use of the UCL Myriad High Performance Computing Facility (Myriad@UCL), and associated support services, in the completion of this work. The authors are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which are partially funded by EPSRC (Grant EP/P020194/1). WMN thanks the DFG for grant NA-686/8 within the priority program SPP 1807 “Control of London Dispersion Interactions in Molecular Chemistry”. EK acknowledges the University of Jyväskylä for access to instrumentation. ...Lisenssi
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