Synthesis of 1-Phosphaspiro[2.n]alkanes by Addition of Terminal Phosphinidene Complexes to Exocyclic Olefins

Academic Article


  • The phosphinidene complexes PhPW(CO)5 (1a) and MePW(CO)5 (1b) have been added to exocyclic olefins to yield 1-phosphaspiro[2.n]alkanes (n = 2−5). The molecular structures of the parent phosphirane 10a and the parent phosphaspiro[2.2]pentane 6a that result from addition of PhPW-(CO)5 to ethylene and methylenecyclopropane, respectively, have been determined by single-crystal X-ray analyses. The reactivity order for addition of both phosphinidene complexes to exocyclic olefins was determined as methylenecyclopentane (4) > methylenecyclobutane (3) > methylenecyclohexane (5) > methylenecyclopropane (2). PhPW(CO)5 is more selective and less reactive in its additions than MePW(CO)5. The relative rates for phosphinidene addition correlate with both 13C NMR chemical shifts of the spiro-carbon and the 1JCH coupling constants of the CH2 group of the 1-phosphaspiro[2.n] alkanes products. © 1993, American Chemical Society. All rights reserved.
  • Authors

    Published In

    Digital Object Identifier (doi)

    Pubmed Id

  • 9533453
  • Author List

  • Hung JT; Yang SW; Gray GM; Lammertsma K
  • Start Page

  • 6786
  • End Page

  • 6790
  • Volume

  • 58
  • Issue

  • 24