2001/01/31 by Masahiro Yamanaka, Eiichi Nakamura · 128 citations
Chemistry · #Catalytic Alkyne Reactions #Synthetic Organic Chemistry Methods #Asymmetric Synthesis and Catalysis #Chemistry #Alkene #Alkyne #Regioselectivity #Insertion reaction #Pauson–Khand reaction #Carbon monoxide #Olefin fiber #Density functional theory #Molecule #Cyclopentenone #Triple bond #Reductive elimination #Metal #Substrate (aquarium) #Photochemistry #Computational chemistry #Stereochemistry #Catalysis #Double bond #Organic chemistry
paper · doi:10.1021/ja005565+
published in Journal of the American Chemical Society 123(8), 1703-1708 (American Chemical Society)
openalex publication_date 2001/01/31 · openalex created_date 2025/10/10 · openalex updated_date 2026/06/26
The Pauson--Khand reaction represents a one-step Co(2)(CO)(8)-catalyzed synthesis of cyclopentenone through [2 + 2 + 1] assembly of one molecule each of alkene, alkyne, and carbon monoxide. Density functional studies (B3LYP/631LAN) on the reaction pathway of the Pauson--Khand (PK) reaction reported here for the first time provides valuable information on the structures and energetics of various intermediates and transition states. The PK reaction consists of olefin insertion, CO insertion, and reductive elimination steps. The olefin insertion step was found to be an irreversible step that determines the stereo- and regiochemistry of the overall reaction. The following steps are low activation energy processes and reversible. The bond-forming events occur only on one of the two metal atoms, while the second metal atom not only acts as an anchor that fixes the metal cluster to the organic substrate but also exerts electronic influences on the reaction at the first atom.