A Cationic Catechol Derivative Binds Anions in Competitive Aqueous Media

A Cationic Catechol Derivative Binds Anions in Competitive Aqueous Media

A simple acyclic molecule binds sulfate strongly (K a>104 M−1) in a competitive 4 : 1 d6-acetone:D2O mixture. The molecule also reacts readily with BF4 and BPh4 to give zwitterions containing an anion tetrahedral boronate centre. These zwitterions were characterised crystallographically.


Abstract

A simple dihydroxy isoquinolinium molecule (3+ ) was prepared by a modification of a literature procedure. Interestingly, during optimisation of the synthesis a small amount of the natural product pseudopalmatine was isolated, and characterised for the first time by X-ray crystallography. Compound 3+ contains a catechol motif and positive charge on the same scaffold and was found to be a potent anion receptor, binding sulfate strongly in 8 : 2 d6-acetone:D2O and 7 : 3 d6-acetone:D2O (K a>104 and 2,100 M−1, respectively). Unsurprisingly, chloride binding was much weaker, even in the less polar solvent mixture 9 : 1 d6-acetone:D2O. The sulfate binding is remarkably strong for such a simple molecule, however anion binding studies were complicated by the tendency of the molecule to react with BPh4 or BF4 species during anion metathesis reactions. This gave two unusual zwitterions containing tetrahedral boronate centres, which were both characterised by X-ray crystallography.