Total Synthesis of the Cephalotaxus Alkaloids. A Problem in Nucleophilic Aromatic Substitution

M. F. Semmelhack, B. P. Chong, R. D. Stauffer, T. D. Rogerson, A. Chong, Lawrence D. Jones

Research output: Contribution to journalArticle

189 Scopus citations

Abstract

The synthesis of cephalotaxine and cephalotaxinone has been achieved in 12-16% overall yield from pyrrolidone and 3,4-methylenedioxyphenylacetic acid. The strategy includes a key step which requires overall intramolecular nucleophilic aromatic substitution of an enolate anion onto an unactivated aromatic ring. Several methods give successful ring closure including addition to a transient aryne (15% yield), coupling via a σ-arylnickel complex (30%), and addition to a transient aryl radical generated from alkali metal reduction (45%) or from irradiation (94%).

Original languageEnglish (US)
Pages (from-to)2507-2516
Number of pages10
JournalJournal of the American Chemical Society
Volume97
Issue number9
DOIs
StatePublished - Apr 1 1975
Externally publishedYes

All Science Journal Classification (ASJC) codes

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

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