Get access

Enantiomerically Pure Phosphaalkene–Oxazolines (PhAk-Ox): Synthesis, Scope and Copolymerization with Styrene

Authors

  • Julien Dugal-Tessier,

    1. Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, V6T 1Z1 (Canada), Fax: (+1) 604-822-2847
    Search for more papers by this author
  • Spencer C. Serin,

    1. Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, V6T 1Z1 (Canada), Fax: (+1) 604-822-2847
    Search for more papers by this author
  • Emmanuel B. Castillo-Contreras,

    1. Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, V6T 1Z1 (Canada), Fax: (+1) 604-822-2847
    Search for more papers by this author
  • Dr. Eamonn D. Conrad,

    1. Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, V6T 1Z1 (Canada), Fax: (+1) 604-822-2847
    Search for more papers by this author
  • Prof. Dr. Gregory R. Dake,

    Corresponding author
    1. Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, V6T 1Z1 (Canada), Fax: (+1) 604-822-2847
    • Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, V6T 1Z1 (Canada), Fax: (+1) 604-822-2847
    Search for more papers by this author
  • Prof. Dr. Derek P. Gates

    Corresponding author
    1. Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, V6T 1Z1 (Canada), Fax: (+1) 604-822-2847
    • Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, V6T 1Z1 (Canada), Fax: (+1) 604-822-2847
    Search for more papers by this author

Abstract

The design of a synthetic route to a class of enantiomerically pure phosphaalkene–oxazolines (PhAk-Ox) is presented. The condensation of a lithium silylphosphide and a ketone (the phospha-Peterson reaction) was used as the P[DOUBLE BOND]C bond-forming step. Attempted condensation of PhC([DOUBLE BOND]O)Ox (Ox=CNOCH(iPr)CH2) and MesP(SiMe3)Li gave the unusual heterocycle (MesP)2C(Ph)[DOUBLE BOND]CN-(S)-CH(iPr)CH2O (3). However, PhAk-Ox (S,E)-MesP[DOUBLE BOND]C(Ph)CMe2Ox (1 a) was successfully prepared by treating MesP(SiMe3)Li with PhC([DOUBLE BOND]O)CMe2Ox (52 %). To demonstrate the modularity and tunability of the phospha-Peterson synthesis several other phosphaalkene–oxazolines were prepared in an analogous manner to 1 a: TripP[DOUBLE BOND]C(Ph)CMe2Ox (1 b; Trip=2,4,6-triisopropylphenyl), 2-iPrC6H4P[DOUBLE BOND]C(Ph)CMe2Ox (1 c), 2-tBuC6H4P[DOUBLE BOND]C(Ph)CMe2Ox (1 d), MesP[DOUBLE BOND]C(4-MeOC6H4)CMe2Ox (1 e), MesP[DOUBLE BOND]C(Ph)C(CH2)4Ox (1 f), and MesP[DOUBLE BOND]C(3,5-(CF3)2C6H3)C(CH2)4Ox (1 g). To evaluate the PhAk-Ox compounds as prospective precursors to chiral phosphine polymers, monomer 1 a and styrene were subjected to radical-initiated copolymerization conditions to afford [{MesPC(Ph)(CMe2Ox)}x{CH2CHPh}y]n (9 a: x=0.13n, y=0.87n; GPC: Mw=7400 g mol−1, PDI=1.15).

Get access to the full text of this article

Ancillary