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Fluorinated Phenanthrenes as Aryne Precursors: PAH Synthesis Based on Domino Ring Assembly Using 1,1‐Difluoroallenes
Author(s) -
Fuchibe Kohei,
Abe Masashi,
Idate Hiroto,
Ichikawa Junji
Publication year - 2020
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.202000069
Subject(s) - phenanthrenes , aryne , domino , ring (chemistry) , chemistry , combinatorial chemistry , organic chemistry , phenanthrene , catalysis
On treatment with the catalyst InBr 3 , 1,1‐difluoroallenes that bear a cyclopentene moiety and an aryl group underwent domino ring assembly in the presence or absence of N ‐bromosuccinimide or N ‐iodosuccinimide to afford aryne precursors such as three‐ringed ortho ‐fluoro(halo)phenanthrenes, four‐ringed ortho ‐fluoro(halo)tetraphenes, ortho ‐fluoro(halo)chrysenes and fluoro[4]helicenes. Metalation of the aryne precursors followed by elimination of the fluoride resulted in the unprecedented systematic generation of arynes bearing π‐extended systems. Diels−Alder reactions of these arynes with isobenzofurans afforded the corresponding cycloadducts whose reductive aromatisation in an SnCl 2 /HBr system furnished fully aromatised benzotriphenylenes. In addition, oxidative aryl−aryl coupling (the Scholl reaction) of these benzotriphenylenes facilitated the synthesis of ‘half HBCs’ (hexabenzocoronenes).