Moorthy, Suresh;
Lambert, Hugues;
Mohan, Neetha;
Schwarzlose, Thomas;
Nau, Werner M;
Kalenius, Elina;
Lee, Tung-Chun;
(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 International Edition
, Article e202303491. 10.1002/anie.202303491.
(In press).
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Abstract
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 β-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.
| Type: | Article |
|---|---|
| Title: | Noncovalent Modulation of Chemoselectivity in the Gas Phase Leads to a Switchover in Reaction Type from Heterolytic to Homolytic to Electrocyclic Cleavage |
| Location: | Germany |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1002/anie.202303491 |
| Publisher version: | https://doi.org/10.1002/anie.202303491 |
| Language: | English |
| Additional information: | © 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/). |
| Keywords: | Cucurbiturils, Gas-Phase Chemistry, Host-Guest Complexes, Mass Spectrometry, Reactivity Modulation |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > MAPS Faculty Office UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > MAPS Faculty Office > Institute for Materials Discovery |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10171339 |
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