The synthesis of aromatic ketones by chromium-catalyzed Kumada arylation of secondary amides with organomagnesium reagents is described. This reaction was enabled by using low-cost chromium­(III) salt as a precatalyst, combined with trimethylsilyl chloride as an additive, and presents a rare example of catalytic transformation of secondary amides to ketones at room temperature. It was shown that catalytically active low-valent chromium species might be responsible for the amide–ketone exchange by mechanism involving the activation of benzimidate intermediate.

Homocoupling of arylboronic acids has been successfully carried out by using the inexpensive simple copper salt CuCl as the catalyst in methanol to obtain symmetric biaryls in good to excellent yields. The reaction proceeds with a CuCl loading of 2 mol‐% under extremely mild conditions: in air, at room temperature, without the need of any additives such as base, oxidant, or ligand.

New CNC pincer-type N-heterocyclic carbene ligands with a central diarylamido moiety are presented. Palladium(II) pincer complexes of type [Pd(L)Cl] (L ) bis[2-(3-alkylimidazolin-2-yliden-1-yl)-4methylphenyl]amido) 5a-c (5a, alkyl ) benzyl; 5b, alkyl ) n-butyl; 5c, alkyl ) 2,4,6-trimethylbenzyl) were obtained from the corresponding silver carbene complexes and [PdCl 2 (MeCN) 2 ] without addition of external bases. The palladium pincer complex 5a was characterized by X-ray diffraction. The molecular structure of 5a shows a distorted square-planar coordination geometry for the palladium atom. Pincer complexes 5a-c have been shown to be active catalysts for the Suzuki-Miyaura reactions.

Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)­(amino)­carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC–Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.