1372785-41-5Relevant articles and documents
Hydrogen-bond-assisted helical folding of propeller-shaped molecules: Effects of extended π-conjugation on chiral selection, conformational stability, and exciton coupling
Opsitnick, Elizabeth A.,Jiang, Xuan,Hollenbeck, Andrew N.,Lee, Dongwhan
supporting information; experimental part, p. 708 - 720 (2012/03/22)
Cooperative interaction between multiple chiral centers dictates the absolute handedness of structural folding. We have designed and prepared a series of chiral C3-symmetric tris(N-salicylidenamine) derivatives that adopt three-blade propeller-like conformations. Synthetic access to an expanded family of such constructs was aided by enzymatic resolution and C-C cross-coupling reactions of aryl-substituted chiral propargylic alcohol derivatives. These key structural components were integrated into molecular propellers of predetermined helical screw sense. Through comparative studies on a homologous set of molecules, we found that installation of phenylene-ethynylene-derived π-conjugation profoundly affected the stabilities of the helically folded structures, as evidenced by UV/Vis and circular dichroism (CD) studies. Increasing the number of hydrogen bonds through additional substitution also enhanced the populations of the folded conformations in solution. In addition to introducing steric bias to control structural folding, linearly π-conjugated groups function as spatially well-defined chromophores that give rise to characteristic exciton-coupled circular dichroism. Absolute configurations of chiral centers could thus be further confirmed by comparing the torsional relationships between pairs of chromophores on adjacent subunits, which are fully consistent with the computationally predicted structural models. Twist to fold: Chiral alcohol groups effectively direct the absolute helicities of three-bladed propeller-shaped C3-symmetric molecules through tight O-H...O-H contacts. The stabilities of the conformations of these systems depend upon the numbers of hydrogen bonds and the steric bulk of the π-conjugated substituents on thestereogenic centers. Copyright