388-06-7Relevant academic research and scientific papers
Fluorinated Phenanthrenes as Aryne Precursors: PAH Synthesis Based on Domino Ring Assembly Using 1,1-Difluoroallenes
Abe, Masashi,Fuchibe, Kohei,Ichikawa, Junji,Idate, Hiroto
, (2020/03/05)
On treatment with the catalyst InBr3, 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 SnCl2/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).
Domino synthesis of fluorine-substituted polycyclic aromatic hydrocarbons: 1,1-difluoroallenes as synthetic platforms
Fuchibe, Kohei,Mayumi, Yuka,Zhao, Nan,Watanabe, Shumpei,Yokota, Misaki,Ichikawa, Junji
, p. 7825 - 7828 (2013/08/23)
Rather crafty: 1,1-Difluoroallenes bearing an aryl group and a cyclopentene moiety undergo indium(III)-catalyzed Friedel-Crafts-type cyclization with subsequent ring expansion and dehydrogenation to afford fluorinated polycyclic aromatic hydrocarbons in high yields. The introduction of an Ar group was effected by in situ halogenation of the intermediary indium species and a subsequent Suzuki-Miyaura reaction. Copyright
