Highly selective Diels-Alder reactions of directly connected enyne dienophiles

Mingji Dai, David Sarlah, Maolin Yu, Samuel J. Danishefsky, Gavin O. Jones, K. N. Houk

Research output: Contribution to journalArticlepeer-review


The paper describes the course of cycloadditions of Diels-Alder dienophiles containing linked enyne sites, each substituted with activating groups. Consistently, it was found that in the enyne cases the Diels-Alder reaction occurred specifically at the acetylenic center. Furthermore, it was found that the regiochemical sense of the cycloaddition was apparently determined by the remote activating group bound to the olefinic site. This remote acrylyl group totally dominated the course of the cycloaddition, relative to the activating group bound directly on the acetylene site. Explanations for these findings at the computational level are provided. The computations also rationalize the strong preference for cycloaddition to occur at the acetylene linkage and encompass the otherwise surprising regiochemical dominance by the remote ester on the olefinic site. The high selectivities available through such reactions provide important new opportunities in the synthesis of orsenillate type substructures that are found in a variety of natural products of contemporary interest.

Original languageEnglish (US)
Pages (from-to)645-657
Number of pages13
JournalJournal of the American Chemical Society
Issue number3
StatePublished - Jan 24 2007
Externally publishedYes

ASJC Scopus subject areas

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


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