69034-12-4Relevant articles and documents
A radical approach to the copper oxidative addition problem: Trifluoromethylation of bromoarenes
Le, Chip,Chen, Tiffany Q.,Liang, Tao,Zhang, Patricia,MacMillan, David W. C.
, p. 1010 - 1014 (2018/06/12)
Transition metal–catalyzed arene functionalization has been widely used for molecular synthesis over the past century. In this arena, copper catalysis has long been considered a privileged platform due to the propensity of high-valent copper to undergo reductive elimination with a wide variety of coupling fragments. However, the sluggish nature of oxidative addition has limited copper’s capacity to broadly facilitate haloarene coupling protocols. Here, we demonstrate that this copper oxidative addition problem can be overcome with an aryl radical–capture mechanism, wherein the aryl radical is generated through a silyl radical halogen abstraction. This strategy was applied to a general trifluoromethylation of aryl bromides through dual copper-photoredox catalysis. Mechanistic studies support the formation of an open-shell aryl species.
Copper-mediated trifluoromethylation of aryl-, heteroaryl-, and vinyltrifluoroborates with Langlois' reagent
Dubbaka, Srinivas Reddy,Salla, Manohar,Bolisetti, Raghu,Nizalapur, Shashidhar
, p. 6496 - 6499 (2014/02/14)
An effortless and realistic procedure for the copper-mediated trifluoromethylation of aryl-, heteroaryl- and vinyltrifluoroborates with CF3 radicals generated from NaSO2CF3 and tert-butyl hydroperoxide (TBHP) is presented. The developed method produces trifluoromethyl arenes and -alkenes in good to excellent yields and a wide range of electronically and structurally diverse substrates are tolerated.
Me3SiCF3/AgF/Cu - A new reagents combination for selective trifluoromethylation of various organic halides by trifluoromethylcopper, CuCF3
Kremlev, Mikhail M.,Mushta, Aleksej I.,Tyrra, Wieland,Yagupolskii, Yurii L.,Naumann, Dieter,M?ller, Angela
scheme or table, p. 67 - 71 (2012/03/10)
An alternative copper halide-free route to obtain highly reactive trifluoromethylcopper species has been developed via the reaction of silver fluoride and trimethyl(trifluoromethyl)silane followed by a redox transmetallation with elemental copper. The composition of the reactive intermediate was investigated by means of UV/Vis/NIR, ESR, 19F NMR spectroscopy and ESI mass spectrometry. "Trifluoromethylcopper" prepared by the oxidative transmetallation route exhibits excellent reactivity and selectivity in substitutions of iodine or bromine bond to aromatic or heterocyclic compounds for trifluoromethyl groups without any additional catalyst.
