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Electrophilic activation of [1.1.1]propellane for the synthesis of nitrogen-substituted bicyclo[1.1.1]pentanes

Abstract:
Strategies commonly used for the synthesis of functionalised bicyclo[1.1.1]pentanes (BCP) rely on the reaction of [1.1.1]propellane with anionic or radical intermediates. In contrast, electrophilic activation has remained a considerable challenge due to the facile decomposition of BCP cations, which has severely limited the applications of this strategy. Herein, we report the electrophilic activation of [1.1.1]propellane in a halogen bond complex, which enables its reaction with electron-neutral nucleophiles such as anilines and azoles to give nitrogen-substituted BCPs that are prominent motifs in drug discovery. A detailed computational analysis indicates that the key halogen bonding interaction promotes nucleophilic attack without sacrificing cage stabilisation. Overall, our work rehabilitates electrophilic activation of [1.1.1]propellane as a valuable strategy for accessing functionalised BCPs.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1002/anie.202111291

Authors

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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
ORCID:
0000-0002-3571-1094
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Role:
Author
ORCID:
0000-0002-4789-7607
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Role:
Author
ORCID:
0000-0003-2869-5855


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Funder identifier:
https://ror.org/0439y7842
Grant:
EP/L015838/1
EP/P020267/1


Publisher:
Wiley
Journal:
Angewandte Chemie International Edition More from this journal
Volume:
61
Issue:
2
Article number:
e202111291
Publication date:
2021-11-26
Acceptance date:
2021-10-27
DOI:
EISSN:
1521-3773
ISSN:
1433-7851
Pmid:
34705316


Language:
English
Keywords:
Pubs id:
1207879
Local pid:
pubs:1207879
Deposit date:
2025-02-28
ARK identifier:

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