Sui Generis Helicene-Based Supramolecular ChirogenicSystem: Enantioselective Sensing Solvent Control and Applicationin Chiral Group Transfer Reaction

摘要

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 = KSS/KRR = 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.