A series of hexa(heteroaryl)benzenes were synthesized by the Ru(II)-carboxylate-catalyzed multiple C-H activation of benzenes carrying pyridyl, pyrimidyl, or pyrazolyl directing groups using N-heteroaryl bromides as coupling partners. The reactions proceeded with high selectivity under microwave irradiation in water. Iterative penta-arylation could be implemented via activation of C-H bonds of generated intermediates by cascade chelation assistance of in situ installed pyridyl groups. This strategy provides multidentate ligands for selective complexation of transition metals and potential building of photoredox systems.

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Efficient diarylation of ortho‐C−H bonds of 2‐arylpyrimidines was achieved by Ru(II)−carboxylate‐catalyzed reaction with aryl bromides in water, whereas meta‐substituted phenylpyrimidines selectively led to monoarylation. The reaction is strongly accelerated under microwave irradiation, and is compatible with various functional groups on both coupling partners. As established from Hammett plots, electron‐withdrawing groups on the pyrimidine substrates facilitate the arylation, while both, electron‐withdrawing and electron‐donating groups on the aryl bromides lead to a faster reaction. The C−H functionalization of 2‐arylpyrimidines with heteroaryl halides provides potential multidentate ligands.

Self-assembly of AgOTf and AgF with the hexatopic ligands hexakis(pyridin-2-yl)benzene (2) and 2,4,6-tris(pyridin-2yl)-1,3,5-tris(quinolin-2-yl)benzene (3) affords the discrete sandwich-shaped complexes [Ag 4 F(2) 2 ](OTf) 3 , [Ag 4 F(3) 2 ]-(OTf) 3 , and [Ag 5 F(2) 2 ](OTf) 4 . The solid-state structures of the complexes were characterized by single-crystal X-ray diffraction analysis, which revealed that the fluoride anion is coordinated in the center of the Ag 4 -square or Ag 5 -pentagon units which are positioned between two molecules of the hexakis(azaheteroaryl)benzene. The generation of complexes is dictated by a unique cooperation of ligand coordination, argentophilicity, and fluoride anion inclusion. All three complexes adopt highly symmetrical structures in solution, as evidenced by appearance of one set of proton resonances for the two ligands arranged face to face.

Two cyclic azomethine imines, 7-methyl- and 7-phenyl-2-oxo-Δ-hexahydropyrazolo[1,5-a]pyridin-8-ium-1-ide, were prepared in seven steps from the respective commercially available δ-keto acids. The addition of Grignard reagents followed by N-alkylation at position 1 afforded the 1,7,7-trisubstituted hexahydropyrazolo[1,5-a]pyridin-2(1H)-ones, whereas 1,3-dipolar cycloadditions of these dipoles to typical acetylenic and olefinic dipolarophiles gave 4a-substituted 2a,2a-diazacyclopenta[cd]indene derivatives as the first representatives of a novel heterocyclic system. Regio- and stereoselectivity as well as the mechanism of these [3 + 2]-cycloadditions were evaluated using computational and experimental methods. The data obtained were in agreement with the polar concerted cycloaddition mechanism via the energetically favorable syn/endo-transition states.