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The Dötz Reaction: A Chromium Fischer Carbene-Mediated Benzannulation Reaction

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Computational Modeling of Homogeneous Catalysis

Part of the book series: Catalysis by Metal Complexes ((CMCO,volume 25))

Abstract

A complete revision of the most widely accepted mechanistic schemes for the Dötz reaction is proposed. According to our calculations the addition of the alkyne molecule to the carbene complex takes place before CO loss in the initial steps of the reaction. Further, our study shows that a novel proposal involving a chromahexatriene intermediate entails lower energy barriers and more stable intermediates than the previous reaction mechanisms postulated by Dötz and Casey. The novel findings query revision of the classically assumed paths and put forward that additional experimental and theoretical studies are necessary to definitely unravel the reaction mechanism of this intringuing reaction.

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References and Notes

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Authors and Affiliations

  1. Institut de Química Computational and Departament de Química, Universitat de Girona, E-17071, Girona, Catalonia, Spain

    Miquel Solà & Miquel Duran

  2. Medicinal Chemistry Dept., Merck Research Laboratories, Merck & Co., West Point, PA

    Maricel Torrent

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  1. Miquel Solà
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  2. Miquel Duran
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  1. Unitat de Química Física, Universitat Autònoma de Barcelona, Bellaterra, Catalonia, Spain

    Feliu Maseras  & Agustí Lledós  & 

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Solà, M., Duran, M., Torrent, M. (2002). The Dötz Reaction: A Chromium Fischer Carbene-Mediated Benzannulation Reaction. In: Maseras, F., Lledós, A. (eds) Computational Modeling of Homogeneous Catalysis. Catalysis by Metal Complexes, vol 25. Springer, Boston, MA. https://doi.org/10.1007/0-306-47718-1_11

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