posted on 2024-01-11, 19:09authored byMengqing Chen, Yuki Itabashi, Shota Fukuma, Rui Shang, Eiichi Nakamura
The indene skeleton is a key structure in a variety of
compounds,
with applications in medicinal and materials science. Traditional
syntheses often require harsh conditions or reactive intermediates
due to the temporary disruption of the aromaticity of the developing
indene ring. To circumvent this problem, we have investigated iron-catalyzed
5-endo-dig cyclization for the construction of the
five-membered carbocycle component of indene, which does not interrupt
the benzene ring’s aromaticity. A reduced iron reactive species
generated by the reduction of FeCl2 with metallic magnesium
is a key reactive species that effectively cleaves the C–O
bond in the starting material to generate a dormant radical-stabilized
iron, which smoothly undergoes the 5-endo-dig closure
of an indene ring. The synthetic conditions are so mild that we synthesized
a high highest occupied molecular orbital (HOMO), narrow bandgap conjugated
compound that has a HOMO level as high as −4.59 eV and an optical
bandgap of 1.50 eV; hence, it is unstable even under air.