Addition of a Terminal Phosphinidene Complex to a Conjugated Diene. Thermal Rearrangement of a Vinylphosphirane to a 1,4-Adduct

Academic Article

Abstract

  • Reaction of the carbene-like terminal phosphinidene complex Ph-P-W(CO) with 1-methoxy-1,3-cyclohexadiene yields in high stereoselectivity a 1,2-addition product, phosphirane 4. Under the reaction conditions 4 subsequently rearranges to a 1,4-adduct, phospholene 5. The [1,3]-sigmatropic shift of the Ph-W-W(CO) group occurs with complete inversion of the sterically crowded P-center. The stereochemistries of the products 4 and 5 have been characterized by single-crystal X-ray structures (4, monoclinic space group P2 /c, a = 11.999 (2) Å, b = 6.720 (3) Å, c = 23.939 (2) Å, β = 99.102 (9)°, Z = 4, R = 4.62%, and R = 6.62%; 5, monoclinic space group P2 /n, a = 16.555 (1) Å, b = 16.860 (2) Å, c = 6.7665 (5) Å, β = 91.96 (5)°, Z = 4, R = 4.35%, and R = 6.26%). © 1992, American Chemical Society. All rights reserved. 5 5 1 w 1 w
  • Authors

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    Digital Object Identifier (doi)

    Author List

  • Lammertsma H; Hung JT; Chand P; Gray GM
  • Start Page

  • 6557
  • End Page

  • 6560
  • Volume

  • 57
  • Issue

  • 24