Sui Generis Helicene-Based Supramolecular Chirogenic System: Enantioselective Sensing, Solvent Control, and Application in Chiral Group Transfer Reaction

[Image: see text] A novel dioxa[6]helicene-based supramolecular chirogenic system (1) as a specific chiral recognition host for enantiopure trans-1,2-cyclohexanediamine (2) is reported. Host 1 with an inherent free phenolic group and a (1S)-camphanate chiral handle on the opposite terminal rings of the helicene chromophore acted as an efficient turn on fluorescent sensor for S,S-2 with an excellent enantioselective factor, α = K(SS)/K(RR) = 6.3 in benzene. This specific host–guest interaction phenomenon is found to be solvent-dependent, which leads to an enantioselective chiral (camphanate) group transfer to the diamine guest molecule. In the case of R,R-2, the de value is up to 68% even at room temperature. Intriguingly, the induced helicity in dioxa[6]helicene diol 6, upon supramolecular hydrogen-bonding interactions, is of opposite sense with positive helicity for S,S-2 and negative helicity for R,R-2, as shown by circular dichroism spectroscopy and in combination with theoretical calculations. This chiral supramolecular system is found to be an excellent host–guest pair for enantiomeric recognition of 2, based on their electronic and steric factors.