121497-50-5Relevant academic research and scientific papers
Polyfluoroorganoboron-oxygen compounds. 2 [1]: Base-catalysed hydrodeboration of polyfluorophenyl(dihydroxy)boranes
Frohn,Adonin,Bardin,Starichenko
, p. 2834 - 2838 (2002)
Polyfluorinated phenyl(dihydroxy)boranes C6H5-nFnB(OH)2 (n = 3 - 5) underwent hydrodeboration (formal replacement of the (dihydroxy)boryl group by hydrogen) in the presence of bases (MeOH, 33% H2O-MeO
Hydrodefluorination of functionalized fluoroaromatics with triethylphosphine: A theoretical and experimental study
Facundo, Aldo A.,Arévalo, Alma,Fundora-Galano, Gabriela,Flores-álamo, Marcos,Orgaz, Emilio,García, Juventino J.
, p. 6897 - 6908 (2019)
Recently we reported the metal free hydrodefluorination of selected fluoroaromatics using triethylphosphine as the sole defluorinating agent. That prompted us to evaluate the mechanistic proposal and in the light of these results, along with new experimental evidence, we have now modified the initial proposal. The new mechanism avoids the highly energetic β-elimination step of roughly 71 kcal mol-1 for hexafluorobenzene and pentafluoropyridine at 393.15 K, invoking the participation of water. The use of D2O confirmed the role of water as the hydrogen source, yielding the corresponding deutero-defluorinated products; DFT calculations agree with this new proposed mechanism. We also report herein the use of this one-pot hydrodefluorination method applied to a broader number of fluoroaromatic derivatives; some of them allowed the collection of key mechanistic evidence.
(NHC)Cu-Catalyzed Mild C-H Amidation of (Hetero)arenes with Deprotectable Carbamates: Scope and Mechanistic Studies
Xie, Weilong,Yoon, Jung Hee,Chang, Sukbok
supporting information, p. 12605 - 12614 (2016/10/07)
Primary arylamines are an important unit broadly found in synthetic, biological, and materials science. Herein we describe the development of a (NHC)Cu system that mediates a direct C-H amidation of (hetero)arenes by using N-chlorocarbamates or their sodio derivatives as the practical amino sources. A facile stoichiometric reaction of reactive copper-aryl intermediates with the amidating reagent led us to isolate key copper arylcarbamate species with the formation of a C-N bond. The use of tBuONa base made this transformation catalytic under mild conditions. The present (NHC)Cu-catalyzed C-H amidation works efficiently and selectively on a large scale over a range of arenes including polyfluorobenzenes, azoles, and quinoline N-oxides. Deprotection of the newly installed carbamate groups such as Boc and Cbz was readily performed to afford the corresponding primary arylamines.
Selective C-F bond activation of tetrafluorobenzenes by nickel(0) with a nitrogen donor analogous to N-heterocyclic carbenes
Doster, Meghan E.,Johnson, Samuel A.
supporting information; experimental part, p. 2185 - 2187 (2009/08/14)
(Chemical Equation Presented) N, not NHC: A neutral, basic, strong σ-donor nitrogen ancillary ligand with properties analogous to those of N-heterocyclic carbenes (NHCs) was developed to aid in the oxidative additions of challenging substrates to late tra
