Nickel-Catalyzed Conjugate Addition of Alkenylzirconium Species to α,β-Unsaturated Ketones

Jeffrey Schwartz, Melanie J. Loots, Hiroshi Kosugi

Research output: Contribution to journalArticle

118 Scopus citations

Abstract

Alkenylzirconium(IV) complexes, prepared by hydrozirconation of the corresponding acetylenes with Cp2Zr(H)Cl (Cp = η5-C5H5), can be utilized in conjugate addition to α,β-enones, catalyzed by Ni(AcAc)2 (AcAc = 2,4-pentanedionate). No 1,2 addition of the alkenyl group is observed, and no trans-cis isomerization occurs. Conjugate addition of terminal alkenyls proceeds faster than that of internal alkenyls. The product of conjugate addition to α-substituted cyclic enones is the trans-1,2-disubstituted cyclic ketone. Attempts to catalyze conjugate addition of alkylzirconium species to α,β-enones using nickel complexes have not been successful. The active form of the catalyst is postulated to be a reduced nickel species, generated by transfer of alkenyl groups from Zr to Ni(II), followed by reductive elimination of diene. It is found that reduction of Ni(AcAc)2 with 1 equiv of DiBAH, prior to reaction, gives an efficient catalyst for improved yields in the case of conjugate addition. Co(AcAc)2 and Pd(AcAc)2/DiBAH were found comparable to Ni(AcAc)2 as effective conjugate addition catalysts. Applications of this conjugate addition reaction to synthesis of prostaglandin analogues are described.

Original languageEnglish (US)
Pages (from-to)1333-1340
Number of pages8
JournalJournal of the American Chemical Society
Volume102
Issue number4
DOIs
StatePublished - Feb 1980

All Science Journal Classification (ASJC) codes

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

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