Liqiuyu

The terminal-selective, remote C(sp³)−H alkylation of alkenes was achieved by a relay process combining NiH-catalyzed hydrometalation, chain walking, and alkylation. This method enables the construction of unfunctionalized C(sp³)−C(sp³) bonds under mild conditions from two simple feedstock chemicals, namely olefins and alkyl halides. The practical value of this transformation is further demonstrated by the large-scale and regioconvergent alkylation of isomeric mixtures of olefins at low catalyst loadings.

The synergistic combination of chain walking, a process involving repeated migratory insertions and β-H eliminations, and cross-coupling chemistry led to the development of a mild, efficient NiH-catalyzed process for the remote hydroalkylation of alkenes. Unfunctionalized C(sp³)−C(sp³) bonds were constructed from two simple feedstock chemicals, namely olefins and alkyl halides.

A palladium(II)-catalyzed γ-C−H amination of cyclic alkyl amines to deliver highly substituted azetidines is reported. The use of a benziodoxole tosylate oxidant in combination with AgOAc was found to be crucial for controlling a selective reductive elimination pathway to the azetidines. The process is tolerant of a range of functional groups, including structural features derived from chiral α-amino alcohols, and leads to the diastereoselective formation of enantiopure azetidines.

Crucial combo: A Pd^II-catalyzed γ-C−H amination of cyclic alkyl amines delivers highly substituted azetidines. The use of a benziodoxole tosylate oxidant in combination with AgOAc was crucial for controlling the selective reductive elimination pathway to the azetidines. The process is tolerant of a range of functional groups, including structural features derived from chiral α-amino alcohols, and leads to the diastereoselective formation of enantiopure azetidines.