Boradigermaallyl: (4+3) Cycloaddition‐Initiated Boron Insertion into Benzene. Issue 18 (24th March 2023)

• Record Type: Journal Article
• Authors: Kern, Ralf H.; Schneider, Meike; Eichele, Klaus; Schubert, Hartmut; Bettinger, Holger F.; Wesemann, Lars
• Is Part Of: Angewandte Chemie international edition. Volume 62:Issue 18(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-03-24
• Subjects: Borylene -- Cycloaddition -- Dienophile -- Germylene -- Insertion; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202301593
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : 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.