In:
Angewandte Chemie, Wiley, Vol. 135, No. 13 ( 2023-03-20)
Abstract:
Electrophilic Al III species have long dominated the aluminum reactivity towards arenes. Recently, nucleophilic low‐valent Al I aluminyl anions have showcased oxidative additions towards arenes C−C and/or C−H bonds. Herein, we communicate compelling evidence of an Al II radical addition reaction to the benzene ring. The electron reduction of a ligand stabilized precursor with KC 8 in benzene furnishes a double addition to the benzene ring instead of a C−H bond activation, producing the corresponding cyclohexa‐1,3(orl,4)‐dienes as Birch‐type reduction product. X‐ray crystallographic analysis, EPR spectroscopy, and DFT results suggest this reactivity proceeds through a stable Al II radical intermediate, whose stability is a consequence of a rigid scaffold in combination with strong steric protection.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v135.13
DOI:
10.1002/ange.202217184
Language:
English
Publisher:
Wiley
Publication Date:
2023
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