Clicking together Alkynes and Tetracyanoethylene
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The [2+2] cycloaddition – retro-electrocyclization (CA-RE) reaction allows ready synthesis of redox-active donor-acceptor chromophores from an electron-rich alkyne and electron-poor olefins like tetracyanoethylene (TCNE). The detailed mechanism of the reaction has been subject of both computational and experimental studies. While several studies point towards a stepwise mechanism via a zwitterionic intermediate for the first step, the cycloaddition, the reaction follows neither simple second-order nor first-order kinetics. Recent studies have shown that the kinetics can be understood if an autocatalytic step is introduced in the mechanism, in which complex formation with the donor-substituted tetracyanobutadiene (TCBD) product possibly facilitates nucleophilic attack of the alkyne onto TCNE, generating the zwitterionic intermediate of the CA step. This Concept highlights the convenient use of the “click-like” CA-RE reaction to obtain elaborate donor-acceptor chromophores and the recent mechanistic results.
Original language | English |
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Article number | e202300236 |
Journal | ChemPhysChem |
Volume | 24 |
Issue number | 15 |
Number of pages | 6 |
ISSN | 1439-4235 |
DOIs | |
Publication status | Published - 2023 |
Bibliographical note
Publisher Copyright:
© 2023 The Authors. ChemPhysChem published by Wiley-VCH GmbH.
- alkynes, chromophores, click chemistry, cycloaddition, retro-electrocyclization
Research areas
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