87639-30-3Relevant academic research and scientific papers
Palladium-Catalyzed Propargylic vs. Allylic Alkylation
Keinan, Ehud,Bosch, Eric
, p. 4006 - 4016 (2007/10/02)
The relative reactivities of allylic propargylic acetates toward palladium(0)-catalyzed substitution by various nucleophiles were studied bu using three types of model substrates: (a) monofunctional allylic and propargylic acetates with similar structural properties; (b) a bifunctional substrate containing both allyl and propargyl functionalities with no apparent interaction between them; (c) conjugated bifunctional systems, in which the two functionalities may interact with one another.Palladium(0)-catalyzed substitution of propargylic acetates by various carbon nucleophiles was found to be less general than the analogous substitution of allylic acetates.Three modes of reactivity were observed, corresponding to three groups of nucleophiles; (a) stabilized carboanions such as sodium dimethyl malonate, which do not react with propargylic acetates but react readily with allylic acetates; (b) nonstabilized organometallics such as phenylzinc chloride, which react with propargylic and allylic acetates at comparable rates (reaction with the former yielding the allenic product exlusively); and (c) allyl- and allenylstannanes, which react with allylic acetates but do not react with isolated propargylic acetates (except for special cases where the propargylic acetate is also an allylic one).Certain similarities between regioselectivity phenomena in organopalladium and organocopper chemistry are discussed.
Organotin Nucleophiles. 5. Palladium-Catalyzed Allylic Propargylation with Allenylstannane
Keinan, Ehud,Peretz, Moshe
, p. 5302 - 5309 (2007/10/02)
Allenyltrialkylstannanes were found to react with various allylic acetates in the presence of catalytic amounts of Pd(PPh3)4 under mild neutral conditions, providing a novel approach for obtaining the 1,5-enyne carbon skeleton.The regioselectivity of propargylation depends largely on the electron-withdrawing properties of the substituents at the two ends of the allylic system: substitution occurs at the end of closer proximity to the more electronegative group.Allylic cyanohydrin acetates are substituted at a position α to the cyano group along with formation of a reduced side product.Several mechanistic aspects of these reactions are discussed.
