103836-53-9Relevant academic research and scientific papers
Reactions of η1-allyl complexes of palladium(II) with electrophiles. Molecular structure of a [2 + 3] cycloadduct of (η1-allyl)palladium with maleic anhydride
Kurosawa, Hideo,Urabe, Akira,Miki, Kunio,Kasai, Nobutami
, p. 2002 - 2008 (2008/10/08)
(η1-Allyl)arylpalladium complexes react with some electrophiles (HCl, Br2, NBS; NBS = N-bromo-succinimide) to give selective Pd-allyl bond cleavage (allylic substitution) with 1,3-transposition, while the corresponding (η3-allyl)arylpalladium analogues react with these electrophiles via selective Pd-Ar bond cleavage. The η1-allyl complexes also react with CCl4 and CHCl3 under very mild conditions to give good yields of CH2=CHCHR(CR′Cl2) (R = H, Me; R′ = Cl, H). Reactions of maleic anhydride with some of the above (η1-allyl)palladium complexes afford 1:1 adducts arising from formal [2 + 3] cycloaddition. The molecular structure of an adduct, PdCHCH2CHC(O)OC(O)CHCH2](C6F 5)((Z)-Ph2PCH=CHPPh2), has been determined by X-ray crystallography. Crystal data: triclinic, space group P1, a = 9.526 (3) A?, b = 14.218 (5) A?, c = 14.122 (5) A?, a = 70.47 (3)°, β = 96.48 (3)°, γ = 92.64 (3)°, and Z = 2. The palladium and the carbonyl substituents are located trans to each other with respect to the five-membered ring. Possible pathways to the cycloadduct are discussed in terms of this stereoselectivity.
