Linear and branched phospha[n]triangulanes

J. Chris Slootweg, Frans J.J. De Kanter, Marius Schakel, Martin Lutz, Anthony L. Spek, Sergei I. Kozhushkov, Armin De Meijere, Koop Lammertsma

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)


Novel, highly stable, linear and branched mono- and diphospha[n]triangulanes were synthesized in high yields by the CuCl-catalyzed phosphinidene addition to spirocyclopropanated methylenecyclopropanes and bicyclopropylidenes. The effect of spirofusion on the electronic properties of these esthetically attractive phosphacycles is apparent from X-ray single crystal structure analyses, which reveals a tightening of the phosphirane ring on additional spirocyclopropanation, and from the NMR features that show deshielded chemical shifts for the ring-phosphorus and -carbon atoms. Steric factors play a role in the addition reaction when the substrate alkene carries a second sphere of spirocyclopropane rings and causes the formation of 2-phosphabicyclo[3.2.0]heptenes in small amounts. These by-products most probably result from addition of the [PhP(Cl)W(CO)5]-Cu-L (L = alkene or solvent) reagent to the spirocyclopropanated bicyclopropylidene to give an intermediate σ-complex, which subsequently, facilitated by steric factors, undergoes a cyclopropylcarbinyl to cyclobutyl ring expansion followed by a [1,3]-sigmatropic shift.

Original languageEnglish
Pages (from-to)6982-6993
Number of pages12
JournalChemistry - A European Journal
Issue number23
Publication statusPublished - 18 Nov 2005
Externally publishedYes


  • Copper
  • Cycloaddition
  • Heterocycles
  • Phosphorus
  • Triangulanes

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry


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