Three molecules of an arylalkyne reacting with a β-amino-substituted α,β-unsaturated Fischer carbene complex to give highly substituted spiro[4.4]nonatrienes

Heiko Schirmer, Bernard L. Flynn, Armin De Meijere

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13 Citations (Scopus)

Abstract

A novel mode of reaction towards arylethynes is shown by the β- trimethylsilyl-substituted α,β-unsaturated Fischer carbene complex 10. A mixture of the isomeric, highly substituted spiro[4.4]nonatrienes 12 and 13 (ratios 1.6:1 to 4.5:1) in yields ranging from 34 to 62% is formed by the formal insertion of three alkyne molecules and concomitant or subsequent cyclization. Such selective triple reactions of alkynes with ethenylcarbene complexes have not previously been observed. It is believed that this reaction proceeds via an unprecedented domino sequence of a formal [3+2] cycloaddition, carbene reformation, and formal [2+2+1] cycloaddition process which occur in conjunction with a number of other additional in situ transformations of transient chromium π-complexes. (C) 2000 Published by Elsevier Science Ltd.

Original languageEnglish
Pages (from-to)4977-4984
Number of pages8
JournalTetrahedron
Volume56
Issue number28
DOIs
Publication statusPublished - 7 Jul 2000
Externally publishedYes

Keywords

  • Fischer carbene complex
  • Metal-carbene
  • Metathesis-type reaction

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