102588-87-4Relevant academic research and scientific papers
Interaction of palladium(0) complexes with allylic acetates, allyl ethers, allyl phenyl chalcogenides, allylic alcohols, and allylamines. Oxidative addition, condensation, disproportionation, and π-complex formation
Yamamoto, Takakazu,Akimoto, Mitsuru,Saito, Osamu,Yamamoto, Akio
, p. 1559 - 1567 (2008/10/08)
Allyl acetate and allyl aryl ether react with Pd(PCy3)2 (1) at room temperature to afford Pd(η3-C3H5)(OY)(PCy3) (Y = acetyl (3), p-cyanophenyl (8)) and [Cy3PCH=CHCH3][OY]. The reaction of 1 with CH2=CHCD2OAc at room temperature leads to the formation of a 1:1 mixture of cis- and trans-Pd(η3-CH2CHCD2)(OAc)(PCy3) accompanied by a 1,3-shift of CH2=CHCD2OAc. Reactions of allyl phenyl sulfide and allyl phenyl selenide with 1 and Pd(P-t-Bu3)2 (2) afford dinuclear Pd2(μ-C3H5)(μ-ZPh)L2 (Z = S, Se) complexes. Reactions of allyl alcohol and 1-methylallyl alcohol with 1 yield Pd(diallyl ether)(PCy3) and Pd(meso-bis(methylallyl) ether)(PCy3), respectively, and mixtures of diallylic ethers. Reactions of crotyl alcohol and 2-methylallyl alcohol with 1 by dismutation give the corresponding aldehyde and alkene; in the case of crotyl alcohol, Pd(crotonaldehyde)(PCy3)2 has been isolated. The reaction of 1 with N-allyltriethylamine bromide affords Pd(η3-C3H5)(Br)(PCy3), whereas the reaction with N-allylaniline affords Pd(N-allylaniline)(PCy3)2. These Pd complexes are not ionic in solutions. Variable-temperature 1H NMR spectra of 3 show fluxional properties of the η3-allyl ligand at room temperature, whereas 8 was found to be rigid. Complexes 3 and 8 react with nucleophiles to afford the corresponding allylated products. Complexes 3 and 8 have the propensity to form binuclear Pd2(μ-C3H5)(μ-OY)(PCy3) 2 complexes in reactions with nucleophiles, PCy3, and 1 and in their thermolysis reactions.
