Boradigermaallyl: (4+3) Cycloaddition‐Initiated Boron Insertion into Benzene

The 2π electron 1,3‐dipole boradigermaallyl, valence‐isoelectronic to an allyl cation, is synthesized from a bis(germylene). It reacts with benzene at room temperature by insertion of a boron atom into the benzene ring. Computational investigation of the mechanism shows the boradigermaallyl reacting...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-04, Vol.62 (18), p.e202301593-n/a
Main Authors: Kern, Ralf H., Schneider, Meike, Eichele, Klaus, Schubert, Hartmut, Bettinger, Holger F., Wesemann, Lars
Format: Article
Language:English
Subjects:
Benzene
Boron
Borylene
Computer applications
Cycloaddition
Dienophile
Dipoles
Germylene
Insertion
Room temperature
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Summary:The 2π electron 1,3‐dipole boradigermaallyl, valence‐isoelectronic to an allyl cation, is synthesized from a bis(germylene). It reacts with benzene at room temperature by insertion of a boron atom into the benzene ring. Computational investigation of the mechanism shows the boradigermaallyl reacting with a benzene molecule in a concerted (4+3) or [π4s+π2s] cycloaddition reaction. Thus, the boradigermaallyl acts as a highly reactive dienophile in this cycloaddition reaction with nonactivated benzene as diene unit. This type of reactivity provides a novel platform for ligand assisted borylene insertion chemistry. Boradigermaallyl featuring a delocalized π‐bond shows a boron atom insertion into benzene at room temperature. The mechanism starts by a concerted (4+3) reaction between the germanium atoms of the digermaboraallyl and the 1,4‐positions of a benzene molecule. Thus, boradigermaallyl acts as a highly reactive dienophile in this cycloaddition reaction with nonactivated benzene.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202301593