- Stereochemistry and mechanism of the ligand-coupling reaction of an optically active acetylacetonato(?-allyl)palladium complex
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The reaction of optically active acetylacetonato(1-methyl-3-phenyl-?-allyl)palladium(II) with triphenylphosphine in THF gave acetylacetone with inversion of configuration, which indicates that the acetylacetonate anion attacked the ?-allyl carbon of a cationic phosphine complex from the side opposite to palladium.
- Hayashi, Tamio,Yamamoto, Akihiro,Ito, Yoshihiko
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- Enantioselective Intermolecular Pd-Catalyzed Hydroalkylation of Acyclic 1,3-Dienes with Activated Pronucleophiles
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We report a highly enantioselective Pd-PHOX-catalyzed intermolecular hydroalkylation of acyclic 1,3-dienes. Meldrum's acid derivatives and other activated C-pronucleophiles, such as β-diketones and malononitriles, react with a variety of aryl- and alkyl-substituted dienes in ≤20 h at room temperature. The coupled products, obtained in up to 96% yield and 97.5:2.5 er, are easily transformed into useful chemical building blocks for downstream synthesis.
- Adamson, Nathan J.,Wilbur, Katherine C. E.,Malcolmson, Steven J.
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supporting information
p. 2761 - 2764
(2018/03/06)
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- Stereo- and Regiochemistry in Palladium-Catalyzed Nucleophilic Substitution of Optically Active (E)- and (Z)-Allyl Acetates
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Optically acive (E)- and (Z)-allyl acetates, 3-acetoxy-1-phenyl-1-butene (1) and its regioisomer, 1-acetoxy-1-phenyl-3-butene (2), were allowed to react with sodium dimethyl malonate, sodium acetylacetonate, and sodium methyl acetoacetate in the presence of a palladium catalyst.The reaction of (E)-acetates proceeded with retention of configuration and that of (Z)-acetates proceeded with inversion accompanied by geometrical isomerization from Z to E.The stereochemistry observed in the reaction with phenylzinc bromide was opposite to that with the soft nucleophiles.
- Hayashi, Tamio,Yamamoto, Akihiro,Hagihara, Toshiya
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p. 723 - 727
(2007/10/02)
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