Controlling dynamic stereoisomerism in transition-metal folded baskets Article

Stojanović, S, Turner, DA, Hadad, CM et al. (2011). Controlling dynamic stereoisomerism in transition-metal folded baskets . CHEMICAL SCIENCE, 2(4), 752-759. 10.1039/c0sc00592d

cited authors

  • Stojanović, S; Turner, DA; Hadad, CM; Badjić, JD

authors

abstract

  • We synthesized chiral molecular baskets (R3/S3)-1, containing three pyridine rings at the rim of a bowlshaped platform. Each pyridine was tethered to the platform via a CH(CH)3 stereogenic center. In line with prior studies, we found that chiral basket (R3)-1 would coordinate to Ag(I) cation forming a Ag(I)- (R3)-1 complex (ΔG° =-5.9 kcal mol-1 at 298.0 K). Furthermore, we used spectroscopic methods (1H NMR, UV-Vis and CD) to establish that the CH(CH)3 stereogenic center with R configuration in Ag(I)-(R3)-1 would direct the twisting of the pyridine rings at the rim in a clockwise orientation (P configuration). UV-Vis and CD spectra of Ag(I)-(R3)-1(P) were also computed (TD-DFT; BHLYP/ SV(P),TZVP), showing good agreement with the experimental data. Controlling dynamic stereoisomerism in basket-like systems is important and the results of this study will be useful for examining the relationship between chiral recognition and reactivity in gated and confined environments. © The Royal Society of Chemistry 2011.

publication date

  • May 9, 2011

published in

Digital Object Identifier (DOI)

start page

  • 752

end page

  • 759

volume

  • 2

issue

  • 4