Boroles from alumoles: accessing boroles with alkyl-substituted backbones transtrielation

• Published in: Chemical science (Cambridge) 2023-08, Vol.14 (34), p.91-915
• Main Authors: Bohlen, Josina L, Endres, Lukas, Drescher, Regina, Radacki, Krzysztof, Dietz, Maximilian, Krummenacher, Ivo, Braunschweig, Holger
• Format: Article
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d3sc02668j

The alumole Cp 3t AlC 4 Et 4 (Cp 3t = 1,2,4-tris( tert -butyl)cyclopentadienyl) is reported to be capable of transferring its butadiene moiety to aryl(dihalo)boranes to generate boroles through aluminum-boron exchange. The products feature a rare alkyl-substituted backbone, which, as shown in other examples, often leads to dimerization due to insufficient steric protection of the antiaromatic borole ring. Sterically crowded aryl groups bound to the boron atom are shown to prevent dimerization, allowing access to the first monomeric derivatives of this type. Results from UV-vis spectroscopy, electrochemistry, and DFT calculations reveal that the alkyl substituents cause remarkable modifications in the optical and electronic properties of the boroles compared to their perarylated counterparts. The synthesis of monomeric 2,3,4,5-tetraalkyl-substituted boroles via metallacycle transfer from an alumole is reported.