Facile [3+2] dimerization and formal dehydrogenative coupling mode of a cyanophenylphosphaallene

Shigekazu Ito, Sou Hashino, Noboru Morita, Masaaki Yoshifuji, Daisuke Hirose, Masae Takahashi, Yoshiyuki Kawazoe

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

Due to a facile head-to-tail [3+2] dimerization, even a sterically demanding group such as the Mes* (2,4,6-tri-tert-butylphenyl) group around the P{double bond, long}C{double bond, long}C moiety did not allow us to isolate 3-(4-cyanophenyl)-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaallene from the elimination reaction of 2-bromo-3-(4-cyanophenyl)-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaprop-1 -ene with DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), and the corresponding 1,4-diphosphafulvene containing cyano groups was obtained and characterized. Theoretical studies on the [3+2] dimerization of phosphaallene characterize possible intermediates affording 1,4-diphosphafulvenes and also suggest the cyano group effect to facilitate the saturation of the P{double bond, long}C double bonds. On the other hand, 1,2-bis(4-cyanophenyl)-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene ]cyclobutene was obtained from 2-bromo-3-(4-cyanophenyl)-3-trimethylsiloxy-1-(2,4,6-tri-tert-butylpheny l)-1-phosphaprop-1-ene together with the 3-(4-cyanophenyl)-1-phosphaallene.

Original languageEnglish
Pages (from-to)10246-10252
Number of pages7
JournalTetrahedron
Volume63
Issue number41
DOIs
Publication statusPublished - 2007 Oct 8

Keywords

  • DFT calculations
  • Oligomerization
  • Phosphaalkenes
  • Phosphorus heterocycles

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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