24255-95-6Relevant articles and documents
Ni-Catalyzed Reductive Cyanation of Aryl Halides and Phenol Derivatives via Transnitrilation
Mills, L. Reginald,Graham, Joshua M.,Patel, Purvish,Rousseaux, Sophie A. L.
supporting information, p. 19257 - 19262 (2019/12/02)
Herein, we report a Ni-catalyzed reductive coupling for the synthesis of benzonitriles from aryl (pseudo)halides and an electrophilic cyanating reagent, 2-methyl-2-phenyl malononitrile (MPMN). MPMN is a bench-stable, carbon-bound electrophilic CN reagent that does not release cyanide under the reaction conditions. A variety of medicinally relevant benzonitriles can be made in good yields. Addition of NaBr to the reaction mixture allows for the use of more challenging aryl electrophiles such as aryl chlorides, tosylates, and triflates. Mechanistic investigations suggest that NaBr plays a role in facilitating oxidative addition with these substrates.
Role of copper in catalyzing aryl and heteroaryl-nitrogen (or -oxygen) bond formation under ligand-free and solvent-free conditions
Basu, Basudeb,Das, Sajal,Mandal, Bablee
experimental part, p. 1701 - 1706 (2009/07/04)
Formation of aryl- or heteroaryl-nitrogen (or -oxygen) bonds under ligand and solvent-free conditions are highly selective to the presence of copper. While bromoarenes undergo C-N (or -O) coupling in stoichiometric presence of copper, heteroaryl bromides require only catalytic amounts of copper(I) salts depending on the position of bromo substituents. Such selectivity coupled with ligand and solvent-free protocols appear promising from the viewpoint of ecology and economy and are more attractive as compared to the existing protocols.
Alkoxy- and amidocarbonylation of functionalised aryl and heteroaryl halides catalysed by a Bedford palladacycle and dppf: A comparison with the primary Pd(II) precursors (PhCN)2PdCl2 and Pd(OAc) 2
Fairlamb, Ian J. S.,Grant, Stephanie,McCormack, Peter,Whittall, John
, p. 859 - 865 (2007/10/03)
The versatility of a Bedford-type palladacycle 1, namely [{Pd(-Cl){κ2-P,C-P(OC6H2-2,4- tBu2)(OC6H3-2,4-tBu 2)2}}2], as a primary Pd source, in combination with the ligand bis-1,1′-(diphenylphosphino)ferrocene (dppf) has been established in carbonylation reactions of aryl and heteroaryl bromides with methanol, piperidine and related nucleophiles. Palladacycle 1 has been compared with other primary Pd sources, e.g. (PhCN)2PdCl2 and Pd(OAc)2. The efficacy of the carbonylation processes appear to be linked to the [Pd] concentration, substrate: catalyst ratio, CO pressure and reaction temperature. In amidocarbonylation, double carbonylation is observed for certain organohalides. In the case of 2,5-dibromopyridine, regioselective amination (Hartwig-Buchwald type) also occurs as a side-reaction. This journal is The Royal Society of Chemistry.