The Role of Chelating Diamine Ligands in the Goldberg Reaction:  A Kinetic Study on the Copper-Catalyzed Amidation of Aryl Iodides

Strieter, Eric R.; Blackmond, Donna G.; Buchwald, Stephen L.

doi:10.1021/ja050120c

Cited by 257 publications

(149 citation statements)

References 14 publications

Supporting

Mentioning

137

Contrasting

Unclassified

Order By: Relevance

“…Cu 2? is known to form strong bonds with diamines [29][30][31]. There are precedents in which amines as reagents produce the collapse of the structure of the MOF acting as catalyst.…”

Section: Resultsmentioning

confidence: 99%

Deactivation of Cu3(BTC)2 in the Synthesis of 2-Phenylquinoxaline

2015

View full text Add to dashboard Cite

Cu 3 (BTC) 2 deactivates by deterioration of its crystal structure during the use of this metal organic framework as catalyst in the synthesis of 2-phenylquinoxaline from phenacylbromide and o-phenylenediamine at room temperature. The material resulting from the use of Cu 3 (BTC) 2 as catalyst was characterized by powder XRD, UV-Vis diffuse reflectance spectra and EPR showing that the crystal structure collapses and Cu 2? becomes reduced under the reaction conditions. Graphical Abstract

show abstract

“…Cu 2? is known to form strong bonds with diamines [29][30][31]. There are precedents in which amines as reagents produce the collapse of the structure of the MOF acting as catalyst.…”

Section: Resultsmentioning

confidence: 99%

Deactivation of Cu3(BTC)2 in the Synthesis of 2-Phenylquinoxaline

2015

View full text Add to dashboard Cite

show abstract

“…For aryl iodides or bromides, a variety of substituents on the benzonitrile moiety, such as Me, OMe, Cl, Br, or CN, can be used. It is worth noting that C-Br or C-Cl compatible with reaction conditions are particularly appealing, since these substituents offer great opportunity for further synthetic manipulations (entries 13,14,16,17,19, and 21, Table 2). The steric hindrance of ortho substituents on the nitrile moiety seemed not to hamper the reaction, and the benzimidazoles could be obtained in excellent yields (entries 7, 8, 13, and 14, Table 2).…”

mentioning

confidence: 99%

Copper-Catalyzed Intramolecular C−N Bond Formation: A Straightforward Synthesis of Benzimidazole Derivatives in Water

et al. 2010

View full text Add to dashboard Cite

A straightforward, efficient, and more sustainable copper-catalyzed method has been developed for intramolecular N-arylation providing the benzimidazole ring system. With Cu(2)O (5 mol %) as the catalyst, DMEDA (10 mol %) as the ligand, and K(2)CO(3) as the base, this protocol was applied to synthesize a small library of benzimidazoles in high yields. Remarkably, the reaction was exclusively carried out in water, rendering the methodology highly valuable from both environmental and economical points of view.

show abstract

“…Lately, we have also contributed to the understanding of this S-arylation reaction mechanism by a In the last twenty years, a particular effort has been addressed to elucidate the mechanistic details concerning the catalytic copper-catalyzed N-, O-, and S-arylations. Thus, Buchwald et al started a program to kinetically investigate the N-arylation of amides and alkylamines [20,21,52,53] and O-arylation of aliphatic alcohols [26,54,55]. They clearly showed that the aryl halide activation occurs by the [(L)Cu I (Nu)] complexes.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Heteroatom Effect on the Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism

et al. 2017

View full text Add to dashboard Cite

Density Functional Theory (DFT) calculations have been carried out in order to unravel the governing reaction mechanism in copper-catalyzed cross-coupling Ullmann type reactions between iodobenzene (1, PhI) and aniline (2-NH, PhNH 2 ), phenol (2-O, PhOH) and thiophenol (2-S, PhSH) with phenanthroline (phen) as the ancillary ligand. Four different pathways for the mechanism were considered namely Oxidative Addition-Reductive Elimination (OA-RE), σ-bond Metathesis (MET), Single Electron Transfer (SET), and Halogen Atom Transfer (HAT). Our results suggest that the OA-RE route, involving Cu III intermediates, is the energetically most favorable pathway for all the systems considered. Interestingly, the rate-determining step is the oxidative addition of the phenyl iodide to the metal center regardless of the nature of the heteroatom. The computed energy barriers in OA increase in the order O < S < NH. Using the Activation Strain Model (ASM) of chemical reactivity, it was found that the strain energy associated with the bending of the copper(I) complex controls the observed reactivity.

show abstract

The Role of Chelating Diamine Ligands in the Goldberg Reaction: A Kinetic Study on the Copper-Catalyzed Amidation of Aryl Iodides

Cited by 257 publications

References 14 publications

Deactivation of Cu3(BTC)2 in the Synthesis of 2-Phenylquinoxaline

Deactivation of Cu3(BTC)2 in the Synthesis of 2-Phenylquinoxaline

Copper-Catalyzed Intramolecular C−N Bond Formation: A Straightforward Synthesis of Benzimidazole Derivatives in Water

Understanding the Heteroatom Effect on the Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism

Contact Info

Product

Resources

About