Deracemization of Carbohelicenes by a Chiral Perylene Bisimide Cyclophane Template Catalyst

Abstract

Deracemization describes the conversion of a racemic mixture of a chiral molecule into an enantioenriched mixture or an enantiopure compound without structural modifications. Herein, we report an inherently chiral perylene bisimide (PBI) cyclophane whose chiral pocket is capable of transforming a racemic mixture of [5]‐helicene into an enantioenriched mixture with an enantiomeric excess of 66 %. UV/Vis and fluorescence titration studies reveal this cyclophane host composed of two helically twisted PBI dyes has high binding affinities for the respective homochiral carbohelicene guests, with outstanding binding constants of up to 3.9×10 ¹⁰  m ⁻¹ for [4]‐helicene. 2D NMR studies and single‐crystal X‐ray analysis demonstrate that the observed strong and enantioselective binding of homochiral carbohelicenes and the successful template‐catalyzed deracemization of [5]‐helicene can be explained by the enzyme‐like perfect shape complementarity of the macrocyclic supramolecular host.

Abstract

An inherently chiral perylene bisimide cyclophane has been synthesized that shows high binding affinities for carbohelicene guests in organic solvents. The perfect shape complementarity of the host–guest system was utilized for the deracemization of conformationally labile [4]‐ and [5]‐helicenes.