4 FLP-Mediated C–H-Activation
165
78. Koester R, Larbig W, Rotermund GW (1965) Pyrolyse von Alkyl- und Cycloalkylboranen.
Liebigs Ann Chem 682:21–48. https://doi.org/10.1002/jlac.19656820103
79. Goldfuss B, Knochel P, Bromm LO, Knapp K (2000) C−H Activation by Direct BoraneHydrocarbon Dehydrogenation: Kinetic and Thermodynamic Aspects. Angew Chem Int Ed
39:4136–4139. https://doi.org/10.1002/1521-3773(20001117)39:22<4136::AID-ANIE4136>
3.0.CO;2-F
80. Légaré M-A, Courtemanche M-A, Rochette É, Fontaine F-G (2015) Metal-Free Catalytic CH Bond Activation and Borylation of Heteroarenes. Science 349:513–516. https://doi.org/10.
1126/science.aab3591
81. Lavergne JL, Jayaraman A, Castro LCM, Rochette É, Fontaine F-G (2017) Metal-Free Borylation of Heteroarenes Using Ambiphilic Aminoboranes: On the Importance of Sterics in
Frustrated Lewis Pair C−H Bond Activation. J Am Chem Soc 139:14714–14723. https://doi.
org/10.1021/jacs.7b08143
82. Chernichenko K, Lindqvist M, Kótai B, Nieger M, Sorochkina K, Pápai I, Repo
T (2016) Metal-Free sp 2 -C−H Borylation as a Common Reactivity Pattern of Frustrated
2-Aminophenylboranes. J Am Chem Soc 138:4860–4868. https://doi.org/10.1021/jacs.6b0
0819
83. Chernichenko K, Nieger M, Leskelä M, Repo T (2012) Hydrogen Activation by 2-Boryl-Ndialkyanilines: a Revision of Piers Ansa-Aminoborane. Dalton Trans 31:9029–9032. https://
doi.org/10.1039/c0dt01716g
84. Quirós MT, Macdonald C, Angulo J, Muñoz MP (2016) Spin Saturation Transfer Difference NMR (SSTD NMR): A New Tool to Obtain Kinetic Parameters of Chemical Exchange
Processes. J Vis Exp 2016:1–13. https://doi.org/10.3791/54499
85. Rochette É, Bouchard N, Légaré Lavergne J, Matta CF, Fontaine F-G (2016) Spontaneous
Reduction of a Hydroborane To Generate a B−B Single Bond by the Use of a Lewis Pair.
Angew Chem Int Ed 55:12722–12726. https://doi.org/10.1002/anie.201605645
86. Rochette É, Boutin H, Fontaine F-G (2017) Frustrated Lewis Pair Catalyzed S−H Bond
Borylation. Organometallics 36:2870–2876. https://doi.org/10.1021/acs.organomet.7b00346
87. Molander GA, Yun CS, Ribagorda M, Biolatto B (2003) B-alkyl Suzuki-Miyaura CrossCoupling Reactions with Air-Stable Potassium Alkyltrifluoroborates. J Org Chem 68:5534–
5539. https://doi.org/10.1021/jo0343331
88. Jayaraman A, Castro LCM, Fontaine F-G (2018) Practical and Scalable Synthesis of Borylated
Heterocycles Using Bench-Stable Precursors of Metal-Free Lewis Pair Catalysts. Org Process
Res Dev 22:1489–1499. https://doi.org/10.1021/acs.oprd.8b00248
89. Bouchard N, Fontaine F-G (2019) Alkylammoniotrifluoroborate Functionalized Polystyrenes:
Polymeric Pre-Catalysts for the Metal-Free Borylation of Heteroarenes. Dalton Trans 48:4846–
4856. https://doi.org/10.1039/c9dt00484j
90. Ren H, Zhou YP, Bai Y, Cui C, Driess M (2017) Cobalt-Catalyzed Regioselective Borylation
of Arenes: N-Heterocyclic Silylene as an Electron Donor in the Metal-Mediated Activation of
C−H Bonds. Chem Eur J 23:5663–5667. https://doi.org/10.1002/chem.201605937
91. Rochette É, Desrosiers V, Soltani Y, Fontaine F-G (2019) Isodesmic C−H Borylation: Perspectives and Proof of Concept of Transfer Borylation Catalysis. J Am Chem Soc 141:12305–12311.
https://doi.org/10.1021/jacs.9b04305
92. Ollivier C, Renaud P (2001) Organoboranes as a Source of Radicals. Chem Rev 101:3415–3434.
https://doi.org/10.1021/cr010001p
93. Ménard G, Hatnean JA, Cowley HJ, Lough AJ, Rawson JM, Stephan DW (2013) C-H Bond
Activation by Radical Ion Pairs Derived from R 3 P/Al(C 6 F 5 ) 3 Frustrated Lewis Pairs and N 2 O.
J Am Chem Soc 135:6446–6449. https://doi.org/10.1021/ja402964h
94. Liu L, (Leo), Cao LL, Shao Y, Ménard G, Stephan DW (2017) A Radical Mechanism for
Frustrated Lewis Pair Reactivity. Chem 3:259–267. https://doi.org/10.1016/j.chempr.2017.
05.022
95. Soltani Y, Dasgupta A, Gazis TA, Ould DMC, Richards E, Slater B, Stefkova K, Vladimirov
VY, Wilkins LC, Willcox D, Melen RL (2020) Radical Reactivity of Frustrated Lewis Pairs with
Diaryl Esters. Cell Reports Phys Sci 1:100016. https://doi.org/10.1016/j.xcrp.2020.100016
165
78. Koester R, Larbig W, Rotermund GW (1965) Pyrolyse von Alkyl- und Cycloalkylboranen.
Liebigs Ann Chem 682:21–48. https://doi.org/10.1002/jlac.19656820103
79. Goldfuss B, Knochel P, Bromm LO, Knapp K (2000) C−H Activation by Direct BoraneHydrocarbon Dehydrogenation: Kinetic and Thermodynamic Aspects. Angew Chem Int Ed
39:4136–4139. https://doi.org/10.1002/1521-3773(20001117)39:22<4136::AID-ANIE4136>
3.0.CO;2-F
80. Légaré M-A, Courtemanche M-A, Rochette É, Fontaine F-G (2015) Metal-Free Catalytic CH Bond Activation and Borylation of Heteroarenes. Science 349:513–516. https://doi.org/10.
1126/science.aab3591
81. Lavergne JL, Jayaraman A, Castro LCM, Rochette É, Fontaine F-G (2017) Metal-Free Borylation of Heteroarenes Using Ambiphilic Aminoboranes: On the Importance of Sterics in
Frustrated Lewis Pair C−H Bond Activation. J Am Chem Soc 139:14714–14723. https://doi.
org/10.1021/jacs.7b08143
82. Chernichenko K, Lindqvist M, Kótai B, Nieger M, Sorochkina K, Pápai I, Repo
T (2016) Metal-Free sp 2 -C−H Borylation as a Common Reactivity Pattern of Frustrated
2-Aminophenylboranes. J Am Chem Soc 138:4860–4868. https://doi.org/10.1021/jacs.6b0
0819
83. Chernichenko K, Nieger M, Leskelä M, Repo T (2012) Hydrogen Activation by 2-Boryl-Ndialkyanilines: a Revision of Piers Ansa-Aminoborane. Dalton Trans 31:9029–9032. https://
doi.org/10.1039/c0dt01716g
84. Quirós MT, Macdonald C, Angulo J, Muñoz MP (2016) Spin Saturation Transfer Difference NMR (SSTD NMR): A New Tool to Obtain Kinetic Parameters of Chemical Exchange
Processes. J Vis Exp 2016:1–13. https://doi.org/10.3791/54499
85. Rochette É, Bouchard N, Légaré Lavergne J, Matta CF, Fontaine F-G (2016) Spontaneous
Reduction of a Hydroborane To Generate a B−B Single Bond by the Use of a Lewis Pair.
Angew Chem Int Ed 55:12722–12726. https://doi.org/10.1002/anie.201605645
86. Rochette É, Boutin H, Fontaine F-G (2017) Frustrated Lewis Pair Catalyzed S−H Bond
Borylation. Organometallics 36:2870–2876. https://doi.org/10.1021/acs.organomet.7b00346
87. Molander GA, Yun CS, Ribagorda M, Biolatto B (2003) B-alkyl Suzuki-Miyaura CrossCoupling Reactions with Air-Stable Potassium Alkyltrifluoroborates. J Org Chem 68:5534–
5539. https://doi.org/10.1021/jo0343331
88. Jayaraman A, Castro LCM, Fontaine F-G (2018) Practical and Scalable Synthesis of Borylated
Heterocycles Using Bench-Stable Precursors of Metal-Free Lewis Pair Catalysts. Org Process
Res Dev 22:1489–1499. https://doi.org/10.1021/acs.oprd.8b00248
89. Bouchard N, Fontaine F-G (2019) Alkylammoniotrifluoroborate Functionalized Polystyrenes:
Polymeric Pre-Catalysts for the Metal-Free Borylation of Heteroarenes. Dalton Trans 48:4846–
4856. https://doi.org/10.1039/c9dt00484j
90. Ren H, Zhou YP, Bai Y, Cui C, Driess M (2017) Cobalt-Catalyzed Regioselective Borylation
of Arenes: N-Heterocyclic Silylene as an Electron Donor in the Metal-Mediated Activation of
C−H Bonds. Chem Eur J 23:5663–5667. https://doi.org/10.1002/chem.201605937
91. Rochette É, Desrosiers V, Soltani Y, Fontaine F-G (2019) Isodesmic C−H Borylation: Perspectives and Proof of Concept of Transfer Borylation Catalysis. J Am Chem Soc 141:12305–12311.
https://doi.org/10.1021/jacs.9b04305
92. Ollivier C, Renaud P (2001) Organoboranes as a Source of Radicals. Chem Rev 101:3415–3434.
https://doi.org/10.1021/cr010001p
93. Ménard G, Hatnean JA, Cowley HJ, Lough AJ, Rawson JM, Stephan DW (2013) C-H Bond
Activation by Radical Ion Pairs Derived from R 3 P/Al(C 6 F 5 ) 3 Frustrated Lewis Pairs and N 2 O.
J Am Chem Soc 135:6446–6449. https://doi.org/10.1021/ja402964h
94. Liu L, (Leo), Cao LL, Shao Y, Ménard G, Stephan DW (2017) A Radical Mechanism for
Frustrated Lewis Pair Reactivity. Chem 3:259–267. https://doi.org/10.1016/j.chempr.2017.
05.022
95. Soltani Y, Dasgupta A, Gazis TA, Ould DMC, Richards E, Slater B, Stefkova K, Vladimirov
VY, Wilkins LC, Willcox D, Melen RL (2020) Radical Reactivity of Frustrated Lewis Pairs with
Diaryl Esters. Cell Reports Phys Sci 1:100016. https://doi.org/10.1016/j.xcrp.2020.100016