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ChemInform Abstract: The Stereochemical Dichotomy in Palladium(0)- and Nickel(0)-Catalyzed Allylic Substitution. by C. N. FARTHING; P. KOCOVSKY is a Chemistry article available to read on EtoBox.

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The Stereochemical Dichotomy in Palladium(0)-and Nickel(0)-Catalyzed Allylic Substitution. -In contrast to the known inversion-inversion steric pathway of allylic esters like (I), the corresponding acetate (IV), containing a phosphinous amide moiety, gives on treatment with malonate (II) in the presence of Pd(0) catalyst a product (V) as result of a retention-inversion pathway by precoordination of the catalyst to the phosphino group rather than to the acetoxy leaving group. While stereochemical control is highly successful with cyclic substrates, it does not operate in acyclic series, as is shown for hexenes (VII) and (X). The Ni(0)-catalyzed reaction of ether (XII) with MeMgBr affords derivative (XV), which is consistent with a double retention pathway. The corresponding trans derivative (XVII) fails to react in the expected manner.

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Author
C. N. FARTHING; P. KOCOVSKY
Publisher
John Wiley and Sons; Wiley (John Wiley & Sons); Wiley (ISSN 0931-7597)
Published
1998
Language
EN
Field
Chemistry (Physical Sciences)

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