Scholl Cyclizations of Aryl Naphthalenes: Rearrangement Precedes Cyclization

The Journal of Organic Chemistry
Sarah L Skraba-JoinerRichard P Johnson

Abstract

In 1910, Scholl, Seer, and Weitzenbock reported the AlCl3-catalyzed cyclization of 1,1'-binaphthyl to perylene. We provide evidence that this classic organic name reaction proceeds through sequential and reversible formation of 1,2'- and 2,2'-binaphthyl isomers. Acid-catalyzed isomerization of 1,1'-binaphthyl to 2,2'-binaphthyl has been noted previously. The superacid trifluoromethanesulfonic acid (TfOH), 1 M in dichloroethane, catalyzes these rearrangements, with slower cyclization to perylene. Minor cyclization products are benzo[k]fluoranthene and benzo[j]fluoranthene. At ambient temperature, the observed equilibrium ratio of 1,1'-binaphthyl, 1,2'-binaphthyl, and 2,2'-binaphthyl is <1:3:97. DFT calculations with the inclusion of solvation support a mechanistic scheme in which ipso-arenium ions are responsible for rearrangements; however, we cannot distinguish between arenium ion and radical cation mechanisms for the cyclization steps. Under similar reaction conditions, 1-phenylnaphthalene interconverts with 2-phenylnaphthalene, with the latter favored at equilibrium (5:95 ratio), and also converts slowly to fluoranthene. Computations again support an arenium ion mechanism for rearrangements.

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Citations

Oct 7, 2016·Chemical Communications : Chem Comm·Maciej KrzeszewskiDaniel T Gryko
Dec 7, 2019·Beilstein Journal of Organic Chemistry·Sarah L Skraba-JoinerRichard P Johnson
May 26, 2018·Chemical Communications : Chem Comm·Irene R MárquezAraceli G Campaña
Dec 7, 2018·Organic Letters·Liqi QiuFrancois Mathey
Nov 15, 2017·The Journal of Organic Chemistry·Sarah L Skraba-JoinerRichard P Johnson
Aug 7, 2019·Organic Letters·Hironobu NakazawaToyoshi Shimada
Oct 13, 2020·Journal of the American Chemical Society·Maggie He, Timothy M Swager
May 16, 2019·The Journal of Organic Chemistry·Alexander M GenaevKonstantin Yu Koltunov

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