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A structural chemistry practitioner: a fox rather than a hedgehog. Reversibility of Friedel–Crafts acyl rearrangements

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Abstract

A retrospective review of reversibility revealed in Friedel–Crafts acyl rearrangements of polycyclic aromatic ketones derived from the polycyclic aromatic hydrocarbons naphthalene, phenanthrene, anthracene, fluorene, pyrene, and fluoranthene is presented. The reactions were carried out in polyphosphoric acid (PPA). A distinction is made between completely reversible reaction (equilibrium reaction) denoted by ⇌ and reaction, both directions denoted by ⇆. Reaction, both direction is considered reversible reaction, not completely reversible reaction. Gore’s 1955 proposition that Friedel–Craft acylation of reactive hydrocarbons is a reversible process has been verified. Complete reversibility has been revealed in ortho ⇌ para acyl rearrangements of fluorofluorenones (1FFL ⇌ 3FFL) and in dibenzofluorenones (DBahFL ⇌ DBbhFL). Both cases are intramolecular acyl rearrangements. The majority of reversible intramolecular and intermolecular Friedel–Crafts acyl rearrangements are formally “reaction, both directions,” e.g., dibenzoylpyrenes 1,6-Bz2PY ⇆ 1,8-Bz2PY. Acyl rearrangements and reversibility in Friedel–Crafts acylations are associated with thermodynamic control. However, sometimes kinetic control wins out over thermodynamic control. Polycyclic aromatic ketones in which the carbonyl group is coplanar with the aromatic nucleus may undergo Friedel–Crafts acyl rearrangements. The reversibility concept has been applied to the synthesis of new and known linearly annelated polycyclic aromatic ketones by intramolecular Friedel–Crafts rearrangements of their angularly annelated constitutional isomers. A linkage between reversible Friedel–Crafts acyl rearrangements in PPA and the Scholl reaction has been established in benzoylnaphthalenes and in dibenzoylpyrenes. As a structural chemistry practitioner, the scientific personality of the first author belongs to the foxes, rather than to the hedgehogs.

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Notes

  1. Πόλλ' οἰδ' ἀλὰπηξ ἀλλ' ἐχῖνος ἕν μέγα. (Diehl, Frag. 103.)

    Isaiah Berlin, “The Hedgehog and the Fox: An Essay on Tolstoy’s View of History,” 1953

  2. First-person singular pronouns refer to Israel Agranat.

  3. It is my (IA) educated guess that the referee who wrote the above report is the late Professor George A Olah, Nobel laureate. I have been young and now am old (Psalms 37:25) and I have just added another sin to the many sins I have committed. Maybe, mitigating circumstances will be found to my disclosing this confidential report: more than two score years have passed since the communication has been reviewed and published and the legendary Professor Olah passed away in 2018 in his 90th year.

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Acknowledgments

Israel Agranat deeply thanks his M.Sc. and Ph.D. students and his other co-workers Yael Asscher, David Avnir, Yael Bentor, Paul Ulrich Biedermann, Benny Bogoslavski, Shmuel Cohen, Hanna Daniel Kraus, Taghreed Hidmi, Liron Levy-Beladev, Tahani Malabi, Yaacov. Netanel Oded, Sergey Pogodin, and Yu-Shan Shih for their essential contributions reported in the present review. “R. Hanina said: I have learnt much from my teachers, and from my colleagues more than from my teachers, but from my students more than from them all” (Babylonian Talmud, Seder Mo‘ed. Tractate Ta'anith, p. 7a).

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  1. Organic Chemistry, Institute of Chemistry, The Hebrew University of Jerusalem, Philadelphia Bldg. #212, Edmond J. Safra Campus, 9190401, Jerusalem, Israel

    Israel Agranat & Tahani Mala’bi

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DEDICATION: In memoriam Professor Peter Henry Gore (1926–2017). Born Heinz Peter Goldfeld in Berlin, he was forced to leave Nazi Germany on the Kindertransport to England in 1939. Gore earned his Ph.D. in Organic Chemistry at Imperial College, was awarded D.Sc. by the University of London, and became Professor of Organic Chemistry at Brunel University (UK). Professor Gore was a Master of Friedel–Crafts Acylations, a brilliant scientist and teacher, and a passionate lover of music. Alas for those who are lost but not forgotten.

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Agranat, I., Mala’bi, T. A structural chemistry practitioner: a fox rather than a hedgehog. Reversibility of Friedel–Crafts acyl rearrangements. Struct Chem 31, 1635–1659 (2020). https://doi.org/10.1007/s11224-020-01593-x

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