120957-65-5Relevant articles and documents
Remarkable stability of copper(II)-N-heterocyclic carbene complexes void of an anionic tether
Lake, Benjamin R. M.,Willans, Charlotte E.
, p. 2027 - 2038 (2014)
A library of pyridyl- and picolyl-substituted imidazolium salts have been synthesized and coordinated to copper, via transmetalation from silver(I)-N-heterocyclic carbenes (NHCs), to prepare several copper(I)- and copper(II)-NHC complexes. The copper(I)-NHCs are complexes of the type Cu(NHC)Br, with the solid-state structures revealing a variety of coordination environments around the copper centers. The stability of the copper(II) complexes is particularly unusual, given the absence of a hard anionic tethering group appended to the ligands. The stability has been attributed to the pyridyl substituent, with the complexes being extremely stable, while those with an appended anionic group tend to be more sensitive to air/moisture. The ligands and complexes have been examined in an Ullmann-type etherification reaction and exhibit improved activity in comparison to copper in the absence of a ligand or the common Cu(I)-NHC complexes Cu(IMes)Cl and [Cu(IMes)2]PF6, indicating stabilization of higher oxidation state species by the ligands during the catalytic cycle.
Phosphazene P4-But base for the Ullmann biaryl ether synthesis
Palomo, Claudio,Oiarbide, Mikel,Lopez, Rosa,Gomez-Bengoa, Enrique
, p. 2091 - 2092 (1998)
In the presence of phosphazene P4-But base and CuBr, aryl halides couple with phenols to give biaryl ethers at ca. 100 °C.
Pd-Catalyzed Etherification of Nitroarenes
Matsushita, Naoki,Kashihara, Myuto,Formica, Michele,Nakao, Yoshiaki
supporting information, p. 2209 - 2214 (2021/07/20)
The Pd-catalyzed etherification of nitroarenes with arenols has been achieved using a new rationally designed ligand. Mechanistic insights were used to design the ligand so that both the oxidative addition and reductive elimination steps of a plausible catalytic cycle were facilitated. The catalytic system established here provides direct access to a range of unsymmetrical diaryl ethers from nitroarenes.
Copper(I)-USY as a Ligand-Free and Recyclable Catalyst for Ullmann-Type O-, N-, S-, and C-Arylation Reactions: Scope and Application to Total Synthesis
Garnier, Tony,Danel, Mathieu,Magné, Valentin,Pujol, Anthony,Bénéteau, Valérie,Pale, Patrick,Chassaing, Stefan
, p. 6408 - 6422 (2018/05/31)
The copper(I)-doped zeolite CuI-USY proved to be a versatile, efficient, and recyclable catalyst for various Ullmann-type coupling reactions. Easy to prepare and cheap, this catalytic material enables the arylation and heteroarylation of diverse O-, N-, S-, and C-nucleophiles under ligand-free conditions while exhibiting large functional group compatibility. The facility of this catalyst to promote C-O bond formation was further demonstrated with the total synthesis of 3-methylobovatol, a naturally occurring diaryl ether of biological relevance. From a mechanistic viewpoint, two competitive pathways depending on the nature of the nucleophile and consistent with the obtained results have been proposed.