Formation and trapping of the thermodynamically unfavoured inverted-hemicucurbit[6]uril.

Formation of inverted-cis-cyclohexanohemicucurbit[6]uril (i-cis-cycHC[6]), with up to 33% isolated yield, can be induced at the expense of thermodynamically favoured cis-cycHC[6]. Reaction selectivity is governed by the solution-based template-aided dynamic combinatorial chemistry and continuous precipitation of the formed macrocycles. Different binding affinities of three diastereomeric cycHC[6]s with trifluoroacetic acid is demonstrated.