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 (R 3/S 3)-1, containing three pyridine rings at the rim of a bowl-shaped 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 (R 3)-1 would coordinate to Ag(i) cation forming a Ag(i)(R 3)-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)-(R 3)-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)-(R 3)-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. © 2011 The Royal Society of Chemistry.

publication date

  • March 14, 2011

published in

Digital Object Identifier (DOI)

start page

  • 752

end page

  • 759

volume

  • 2

issue

  • 4