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Formation of Perylenes by Oxidative Dimerization of Naphthalenes Bearing Radical Sources
Author(s) -
Hirao Yasukazu,
Okuda Tomoki,
Hamamoto Yosuke,
Kubo Takashi
Publication year - 2020
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201900620
Subject(s) - chemistry , naphthalene , moiety , phenol , photochemistry , perylene , oxidative phosphorylation , biphenyl , oxidative coupling of methane , intermolecular force , radical ion , ring (chemistry) , derivative (finance) , medicinal chemistry , organic chemistry , molecule , catalysis , ion , biochemistry , financial economics , economics
The introduction of phenol groups at the 1,8‐positions of naphthalene allowed its one‐pot oxidative dimerization and subsequent oxidative cyclization to the perylene structures under mild conditions and upon addition of iron (III) chloride. Examination using various derivatives and DFT calculations revealed that these reactions are initiated by the oxidation of the phenol moiety to generate a radical cation, which is supplied as a radical source for the reactions. The delocalization of the spin density from the radical cation of the introduced phenol groups to the naphthalene ring is proposed to be responsible for the intermolecular oxidative homo‐coupling reactions at the peri ‐positions of the naphthalene and the subsequent oxidative cyclization at the 8,8’‐positions of the 1,1’‐binaphthyl derivative.