Synthesis and Reactivity of 2‐Arylquinazoline Halidoruthenacycles in Arylation Reactions

@article{Kuzman2017SynthesisAR,
  title={Synthesis and Reactivity of 2‐Arylquinazoline Halidoruthenacycles in Arylation Reactions},
  author={Petra Kuzman and Franc Po{\vz}gan and Anton Meden and Jurij Svete and Bogdan {\vS}tefane},
  journal={ChemCatChem},
  year={2017},
  volume={9}
}
The synthesis of a range of new cyclometallated organoruthenium(II) complexes through the ortho‐C−H activation of the aryl group in 2‐aryl‐substituted quinazolines with [RuX2(p‐cymene)]2 is described. The beneficial effect of the carboxylate ligand on both the cyclometallation and the further arylation reaction step was demonstrated. Mechanistic studies reveal that bromide and iodide anions decelerate the arylation process by an in situ ligand exchange reaction. Additionally, a detailed NMR… 
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11 Citations

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References

SHOWING 1-10 OF 105 REFERENCES
Ru-Catalysed C–H Arylation of Indoles and Pyrroles with Boronic Acids: Scope and Mechanistic Studies
TLDR
The Ru-catalysed C2–H arylation of indoles and pyrroles by using boronic acids under oxidative conditions is reported and Mechanistic studies suggest the on-cycle intermediates do not possess a para-cymene ligand and that theOn-cycle metalation occurs through an electrophilic attack by the Ru centre.
C–H Bond Functionalization of Arylpyrimidines Catalyzed by an in situ Generated Ruthenium(II) Carboxylate System and the Construction of Tris(heteroaryl)‐Substituted Benzenes
A ruthenium(II) carboxylate catalyst, generated in situ from [RuCl 2 (p-cymene)] 2 and 1-phenyl-1-cyclopentanecarboxylic acid (PCCA) in the presence of K 2 CO 3 , allowed activation of the C―H bond…
Carboxylate-assisted ruthenium(II)-catalyzed C–H arylations of 5-aryl tetrazoles: step-economical access to Valsartan
Ruthenium‐Catalyzed C−H Arylation of Benzoic Acids and Indole Carboxylic Acids with Aryl Halides
TLDR
The first Ru‐catalyzed C−H arylation of benzoic acids with readily available aryl (pseudo)halides with efficiently applied protocol can efficiently be applied to indole carboxylic acids, thus allowing access to C7‐, C6‐,C5‐ and C4‐arylated indole compounds.
Quinazoline‐Directed C–H Bond Functionalization Catalyzed by Ruthenium(II) Carboxylate – Construction of Polyconjugated Aryl‐Heteroaryl Systems
A series of coupling products have been prepared by a ruthenium(II)-catalyzed direct ortho-C–H arylation of 2-(aryl/heteroaryl)-substituted quinazolines with (hetero)aryl bromides.…
Cycloruthenation of aryl imines and N-heteroaryl benzenes via C–H bond activation with Ru(II) and acetate partners
Palladium-catalyzed ortho-arylation of benzamides via direct sp(2) C-H bond activation.
The palladium-catalyzed ortho-arylation of benzamides by aryl iodides has been demonstrated with the simplest amide CONH(2) as a directing group for the first time. This protocol can be applied to…
Carbon-hydrogen bond functionalization approach for the synthesis of fluorenones and ortho-arylated benzonitriles.
A sequence consisting of palladium-catalyzed benzamide ortho-arylation/reaction with (CF3CO)2O was developed allowing a convenient one-pot synthesis of ortho-arylated benzonitriles and fluorenone…
Pd-catalyzed ortho-arylation of phenylacetamides, benzamides, and anilides with simple arenes using sodium persulfate
We report a mild and efficient Pd-catalyzed ortho-arylation of phenylacetamides, benzamides, and anilides with a range of simple arenes using sodium persulfate (Na2S2O8). This green strategy…
Ru-Catalyzed C–H Arylation of Fluoroarenes with Aryl Halides
TLDR
Deuterium labeling and kinetic isotope effect experiments indicate that C–H activation is both reversible and kinetically significant and Computational studies support a concerted metalation–deprotonation (CMD)-type ruthenation mode and shed light on the unusual arylation regioselectivity.
...
1
2
3
4
5
...