2010/12/23 by Jonatan Kleimark, Charlotte Johansson, Susanne Olsson +4 · 1 voice · 15 citations
Chemistry · #Alkyl #Allylic rearrangement #Asymmetric Hydrogenation and Catalysis #Asymmetric Synthesis and Catalysis #Catalysis #Catalytic C–H Functionalization Methods #Chemistry #Dimethyl malonate #Ligand (biochemistry) #Malonate #Medicinal chemistry #Moiety #Nucleophile #Organic chemistry #Palladium #Regioselectivity #Selectivity #Stereochemistry #Steric effects #Substituent #Tsuji–Trost reaction
paper · doi:10.1021/om1007264
published in Organometallics 30(2), 230-238 (American Chemical Society)
openalex publication_date 2010/12/23 · openalex created_date 2025/10/10 · openalex updated_date 2026/06/15
The selectivity in the Pd-assisted allylic alkylation has been investigated in a system with a ligand tethered to the allylic moiety. Isolation of (η 3 -allyl)Pd complexes and stoichiometric reaction with malonate nucleophiles allowed separation of various factors influencing the regioselectivity in a system that cannot undergo apparent rotation. Unexpectedly, trans effects were found to have only a minor influence on the selectivity, whereas changing the tether length could shift the preference from favored internal to dominant terminal attack. DFT-assisted analysis revealed that the dominant selectivity-determining factors are the forced rotation of the allylic moiety and an important steric repulsion from a syn- alkyl substituent.