Top Organomet Chem (2020) 67: 39–56
https://doi.org/10.1007/3418_2020_45
# Springer Nature Switzerland AG 2020
Published online: 2 June 2020
Mechanisms of Metal-Catalyzed
Electrophilic F/CF 3 /SCF 3 Transfer
Reactions from Quantum Chemical
Calculations
Binh Khanh Mai and Fahmi Himo
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2 Technical Details . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . .. . . . . 41
3 Zinc-Catalyzed Aminofluorination of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4 Rhodium-Catalyzed Oxyfluorination and Trifluoromethylation of Diazocarbonyl
Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
5 Reactions with N–F and N–SCF 3 Reagents . . . . . . .. . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . .. . . 49
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Abstract Electrophilic F/CF 3 /SCF 3 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/CF 3 /SCF 3 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 fluorinecontaining groups.
B. K. Mai and F. Himo (*)
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm,
Sweden
e-mail: fahmi.himo@su.se
https://doi.org/10.1007/3418_2020_45
# Springer Nature Switzerland AG 2020
Published online: 2 June 2020
Mechanisms of Metal-Catalyzed
Electrophilic F/CF 3 /SCF 3 Transfer
Reactions from Quantum Chemical
Calculations
Binh Khanh Mai and Fahmi Himo
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2 Technical Details . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . .. . . . . 41
3 Zinc-Catalyzed Aminofluorination of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4 Rhodium-Catalyzed Oxyfluorination and Trifluoromethylation of Diazocarbonyl
Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
5 Reactions with N–F and N–SCF 3 Reagents . . . . . . .. . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . .. . . 49
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Abstract Electrophilic F/CF 3 /SCF 3 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/CF 3 /SCF 3 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 fluorinecontaining groups.
B. K. Mai and F. Himo (*)
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm,
Sweden
e-mail: fahmi.himo@su.se