Rendering classical hydrophilic enantiopure Werner salts [M(en) 3 ] n+ n X − lipophilic (M/ n = Cr/3, Co/3, Rh/3, Ir/3, Pt/4); new chiral hydrogen bond donor catalysts and enantioselectivities as a function of metal and charge Academic Article uri icon

abstract

  • Known hydrophilic halide salts of the title compounds are converted to new lipophilic BArf- (B(3,5-C6H3(CF3)2)4-) salts. These are isolated as hydrates (Λ- or Δ-[M(en)3]n+nBArf-·zH2O; z = 17-9) and characterized by NMR (acetone-d6) and microanalyses. Thermal stabilities are probed by capillary thermolyses and TGA and DSC measurements (onset of dehydration 71-151 °C). In the presence of tertiary amines, they are effective catalysts for enantioselective Michael type carbon-carbon or carbon-nitrogen bond forming additions of 1,3-dicarbonyl compounds (acceptors: trans-β-nitrostyrene, di-tert-butylazodicarboxylate, 2-cyclopenten-1-one; average ee = 33%, 52%, 17%). Effects of the metal and charge upon enantioselectivities are analyzed. A number of properties appear to correlate to the NH Brønsted acidity order ([Pt(en)3]4+ > [Cr(en)3]3+ > [Co(en)3]3+ > [Rh(en)3]3+ > [Ir(en)3]3+).

author list (cited authors)

  • Maximuck, W. J., Ganzmann, C., Alvi, S., Hooda, K. R., & Gladysz, J. A.

citation count

  • 6

publication date

  • March 2020