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Mechanisms of Metal-Catalyzed Electrophilic F/CF3/SCF3 Transfer Reactions from Quantum Chemical Calculations

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New Directions in the Modeling of Organometallic Reactions

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 67))

Abstract

Electrophilic F/CF3/SCF3 transfer reactions have recently emerged as a promising strategy to introduce fluorine substituents to organic compounds at mild conditions with high reactivity and selectivity. Several safe and stable electrophilic reagents have been introduced and have found interesting applications in synthetic chemistry. To control the reactivity and selectivity of these reactions, metal catalysts are typically used in combination with the reagents. Herein, we describe our recent efforts to elucidate the detailed mechanisms and origins of selectivity for a number of metal-catalyzed electrophilic F/CF3/SCF3 transfer reactions using density functional theory calculations. Focus is on reactions employing hypervalent fluoroiodine and nitrogen-based reagents, with zinc or rhodium as the metal catalysts. The roles of the metal ions are discussed, and some novel mechanistic ideas have emerged from these calculations that can have bearing on other reactions for introducing fluorine-containing groups.

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Acknowledgment

We thank co-workers and collaborators who contributed to this work, in particular Dr. Jiji Zhang and Prof. Kálmán J. Szabó. BKM thanks the Carl-Trygger Foundation for a postdoctoral fellowship. We thank the Knut and Alice Wallenberg Foundation (Dnr: 2018.0066) for financial support.

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Authors and Affiliations

  1. Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm, Sweden

    Binh Khanh Mai & Fahmi Himo

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  1. Binh Khanh Mai
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  2. Fahmi Himo
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Correspondence to Fahmi Himo .

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Editors and Affiliations

  1. Departament de Química, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, Barcelona, Spain

    Agustí Lledós

  2. Departament de Química, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, Barcelona, Spain

    Gregori Ujaque

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Mai, B.K., Himo, F. (2020). Mechanisms of Metal-Catalyzed Electrophilic F/CF3/SCF3 Transfer Reactions from Quantum Chemical Calculations. In: Lledós, A., Ujaque, G. (eds) New Directions in the Modeling of Organometallic Reactions. Topics in Organometallic Chemistry, vol 67. Springer, Cham. https://doi.org/10.1007/3418_2020_45

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