The Ni-catalyzed reaction of ortho-phenoxy-substituted aromatic amides with alkynes in the presence of LiOtBu as a base results in C–O/N–H annulation with the formation of 1(2H)-isoquinolinones.

The nickel-catalyzed reductive cleavage of esters in the absence of an external reductant, which involves the cleavage of an inert acyl C–O bond in O-alkyl esters is reported.

The iridium‐catalyzed reaction of imidazoles with formates in the presence of hydrosilanes as coreactants led to the production of 2‐[(alkoxy)(siloxy)methyl]imidazoles. Dimethyl acetylenedicarboxylate was the additive of choice for the reaction in terms of reaction efficiency. No reaction was observed in the absence of the hydrosilanes. Whereas substituents at the 1‐ and 5‐positions on the imidazole ring did not affect the reaction, substituents at the 4‐position greatly retarded the reaction. The regioselective reaction of 1‐methyl‐1,2,4‐triazole occurred at the carbon atom between the sp3 and sp2 nitrogen atoms of the ring but not between two sp2 nitrogen atoms. The products were converted into imidazole 2‐carbaldehydes by hydrolysis under acidic conditions.

The combination of TpRh(C2H4)2 (Tp = tris(pyrazol-1-yl)borate) and P(2-furyl)3 catalyzes the reaction of tertiary alkyl-substituted alkynes with tert-butylhydrazine, leading to the formation of 3,3,3-trisubstituted propionitrile derivatives. This reaction system is applicable to 1,1-disubstituted propargyl alcohols and amines to afford the corresponding β-cyanohydrins and β-amino nitriles, respectively. The catalytic cycle involves the formation of a vinylidenerhodium complex as a key intermediate.

An efficient Suzuki‐Miyaura cross‐coupling reaction of ortho‐phenoxy‐substituted aromatic amides with aryl boronates is described. The use of LiOtBu is crucial for the success of the reaction. An amidate anion, which is formed through deprotonation of the amide NH bond by LiOtBu, functions as a directing group to activate a C−O bond.