Direct coupling of ethers and acyl halides was promoted by a binary catalytic system comprising an Ir-based photocatalyst and a Ni complex under blue-light irradiation. Photocatalysts with high triplet energy directed the catalysis, and the reaction likely proceeded by triplet-triplet energy transfer from the excited photocatalysts. Chlorine radicals generated from an excited Ni complex bearing a Ni-Cl bond would be responsible for generating α-oxy radicals leading to the α-acylated ethers.

A direct aldol reaction of an α-azido 7-azaindolinylamide, promoted by a Cu-based cooperative catalyst, is documented. Aromatic aldehydes bearing an ortho substituent exhibited diastereodivergency depending on the nature of the chiral ligands used. Smooth reactions with ynals highlighted the broad substrate scope. A vicinal azido alcohol unit in the product allowed direct access to the corresponding aziridine and facile hydrolysis of the 7-azaindolinylamide moiety furnished enantioenriched β-hydroxy-α-azido carboxylic acid derivatives.

An α-N3 7-azaindoline amide serves as a latent enolate to directly engage in an asymmetric Mannich-type reaction with N-thiophosphinoyl imines by the action of a cooperative catalyst. The thus-obtained highly enantioenriched anti-adduct was transformed into β-amino-α-azido acid in high yield by simple acidic treatment.

Nickel(0)-promoted carboxylation of aryl ynol ether proceeded in a highly regioselective manner to produce α-substituted-β-aryloxyacrylic acid derivatives. The α-substituted-β-aryloxyacrylic acids were transformed into the corresponding β-aryloxypropionic acid derivative as an optically active form via rhodium-catalyzed asymmetric hydrogenation.

A direct aldol reaction of an a-azido 7-azaindolinylamide, promoted by a Cu-based cooperative catalyst, is documented. Aromatic aldehydes bearing an ortho substituent exhibited diastereodivergency depending on the nature of the chiral ligands used. Smooth reactions with ynals highlighted the broad substrate scope. A vicinal azido alcohol unit in the product allowed direct access to the corresponding aziridine and facile hydrolysis of the 7-azaindolinylamide moiety furnished enantioenriched b-hydroxy-a-azido carboxylic acid derivatives.