2024/09/18 by Marianna Danopoulou, Leandros P. Zorba, Athanasia P. Karantoni +2 · 1 voice
Chemistry · #Asymmetric Hydrogenation and Catalysis #Asymmetric Synthesis and Catalysis #Catalytic C–H Functionalization Methods
paper · pdf · doi:10.1021/acs.joc.4c01662
openalex publication_date 2024/09/18 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/25
High Resolution Image Download MS PowerPoint Slide A highly efficient, in situ formed CuCl 2 /TMEDA catalytic system (TMEDA = N, N, N ′, N ′-tetramethylethylene-diamine) for the cross-coupling reaction of aryl acetonitriles with benzyl alcohols is reported. This user-friendly protocol, employing a low catalyst loading and a catalytic amount of base, leads to the synthesis of α-alkylated nitriles in up to 99% yield. Experimental mechanistic investigations reveal that the key step of this transformation is the C(sp 3 )–H functionalization of the alcohol, taking place via a hydrogen atom abstraction, with the simultaneous formation of copper-hydride species. Detailed density functional theory studies shed light on all reaction steps, confirming the catalytic pathway proposed on the basis of the experimental findings.