Copper-catalyzed cross-coupling of diethyl phosphonate with aryl iodides

Abstract

Cross-coupling of diethyl phosphonate with aryl iodides was performed using copper(I) iodide complexes with various bidentate ligands as catalysts.Resurgence of Ullmann chemistry led to development of catalytic methods for formation of new carbon-carbon bonds with the use of various copper complexes and especially strongly affected development of reactions involving formation of carbonheteroatom bonds, in particular bonds between aromatic or vinyl carbon atoms and sulfur, selenium, oxygen, nitrogen, and phosphorus. The formation of the latter was studied most poorly.After pioneering study by Gelman and Buchwald [1], where phosphorylation of aryl and vinyl iodides and vinyl bromides with dibutyl phosphonate was catalyzed by CuI with N,N′-dimethylethane-1,2-diamine (I) as ligand, Fu H. and co-workers [2, 3] reported on the synthesis of arylphosphonates, arylphosphinates, and arylphosphine oxides under catalysis by CuI complexes with proline (II), piperidine-2-carboxylic acid (III), and phenyl hydrogen pyrrolidin-2-ylphosphonate (IV) at 110°C. All these reactions required large amounts of CuI (10-20 mol %) and ligand (20-40 mol %) and long time (up to 36 h). The reactions of diphenylphosphine oxide and dibutyl and diisopropyl phosphonates with 2-bromotrifluoroacetanilide in the presence of N-methylpyrrolidine-2-carboxamide (V) as ligand were carried out at lower temperature (50°C), but a high concentration of CuI (30 mol %) and equimolar amount of the ligand (100 mol %) were necessary [4].

Stereoselective Synthesis of Phosphoryl‐Substituted Phenols

“…It is deduced that ArCls are too unreactive toward oxidative addition, and when the phenolate is absent or too stable, the reaction does not work. Compared with the previous report, the present catalytic system shows the advantage that some aryl halides can react with P(O)H compounds efficiently without the use of some special ligands 8f–o…”

“…Although some significant achievements in the palladium‐catalyzed formation of PC bonds have been made, the drawbacks of the catalyst systems, such as sensitivity to air, high cost, and toxicity, limit their applications 8d–e. During the past decade, great progress in the copper‐catalyzed phosphorylation of aryl and vinyl iodides has also been achieved 8f–o. Buchwald and Wiemer investigated the cross‐coupling of vinyl bromides with dibutyl phosphonate via the assistance of CuI and N , N′ ‐dimethylethane‐1,2‐diamine in 2003 8k,r.…”

Transition Metal Exchanged Hydroxyapatite/Fluorapatite Catalysts for C−C and C−N Bond Forming Reactions

“…Copper is one of the cheapest and widely used transition metal catalyst in coupling chemistry [26] . The introduction of N‐arylation of heterocycles by Buchwald [12,27,28] and Taillefer [29,30] using bromo‐ and iodoarenes with copper catalyst in presence of a basic ligand paved interest of chemists all over the globe.…”

Focusing on the Catalysts of the Pd- and Ni-Catalyzed Hirao Reactions

“…The protocol was extended to H -phosphinates, as well as secondary phosphine oxides applying a wide range of arenes [ 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ]. Later on, Ni- and Cu complexes were also used as catalysts [ 10 , 11 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 ]. Green chemical approaches, including microwave (MW)-assistance [ 32 , 33 , 34 , 35 , 36 , 37 ] and phase transfer catalysis, were also elaborated [ 38 , 39 , 40 , 41 ].…”