Total Synthesis of Hamigerans and Analogues Thereof. Photochemical Generation and Diels-Alder Trapping of Hydroxy-o-quinodimethanes

K. C. Nicolaou, David L.F. Gray, Jinsung Tae

Research output: Contribution to journalArticle

130 Citations (Scopus)

Abstract

A number of naturally occurring substances, including hamigerans, contain ring systems which are fused to an aromatic nucleus. A general and streamlined method for the construction of such benzannulated bi- and polycyclic carbon frameworks has been developed, and its scope and limitations were explored. On the basis of the photoenolization of substituted benzaldehydes and subsequent Diels-Alder (PEDA) trapping of the generated hydroxy-o-quinodimethanes, this method was optimized to set the stage for the total synthesis of several naturally occurring members of the hamigeran class. Specifically, the developed synthetic technology served as the centerpiece process for the successful asymmetric synthesis of hamigerans A (2), B (3), and E (7). In addition to the PEDA reactions, several other novel reaction processes are described, including a high-yielding decarbonylative ring contraction and an oxidative decarboxylation of a hydroxyl β-keto ester to afford an α-diketone. A number of analogues of these biologically active natural products were also prepared by application of the developed technology.

Original languageEnglish
Pages (from-to)613-627
Number of pages15
JournalJournal of the American Chemical Society
Volume126
Issue number2
DOIs
Publication statusPublished - 2004 Jan 21

All Science Journal Classification (ASJC) codes

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

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