Regiocontrolled Coupling of (π-Allylic)palladium Complexes with Organozirconium Species

James S. Temple, Martin Riediker, Jeffrey Schwartz

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Abstract

A carbon-carbon bond-forming reaction has been developed involving coupling between an alkenylzirconium(IV) complex, prepared by hydrozirconation of the corresponding terminal acetylene, and (η3-allylic)palladium chloride dimers, prepared from olefins, to give 1,4 dienes. A stereospecific synthesis of 20(R)-cholestan-3-one is described. Bis(η5-cyclo-pentadienyl)chloro(4′-methylpent-1′-en-1′-yl)zirconium reacts with di-μ-chloro-bis[η3-16,17,20-(3-oxopregn-17(20)(Z)-en-16-yl ethylene ketal)]dipalladium in the presence of maleic anhydride. A mixture is obtained consisting of 1,4 dienes produced by addition of the alkenyl group to either the C(20) or C(16) terminus, respectively, of the allylic system. Hydrogenation of the C(20)-coupled product and deketalization yielded 20(R)-cholestanone exclusively. Transfer of the organic group from zirconium to palladium precedes carbon-carbon bond formation; this result is shown to be valid both in the presence and in the absence of added ligand. Coupled product thus obtained has stereochemistry opposite to that formed by stabilized anion attack on η3-allylic complexes of palladium. The analogous sequence, starting from the epimeric di-μ-chloro-bisη3-16,17,20-(3-oxopregn-17(20)(E)-en-16-yl ethylene ketal)]dipalladium, yielded 20(S)-cholestanone exclusively. It was observed that regioselectivity of coupling depends on the nature of palladium ligands present. This phenomenon is rationalized by postulating the intermediacy of isomeric square-planar (η3-allyl)palladium(alkenyl)(ligand) complexes, which subsequently reductively eliminate allyl-alkenyl (1,4 diene) with concomitant extrusion of palladium(0).

Original languageEnglish (US)
Pages (from-to)1310-1315
Number of pages6
JournalJournal of the American Chemical Society
Volume104
Issue number5
DOIs
StatePublished - Jan 1 1982

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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