The Bull-James assembly: Efficient iminoboronate complex formation for chiral derivatization and supramolecular assembly

[Display omitted] •Development of the assembly of iminoboronate ester (IBE) complexes is discussed.•IBE chiral derivatization to measure the ee of a range of analytes is catalogued.•Use of NMR, optical, and electrochemical methods for chiral analysis is presented.•IBE-derived materials exhibit dynamic and stimuli-responsive properties.•Iminoboronates can be used for the bioorthogonal labelling of biomolecules. Chiral molecules are widely used in many fields of research and so practically simple, accurate methods to measure their enantiopurities are required. This review’s initial focus is on one such method, the Bull-James assembly, which employs a three-component protocol combining 2-formylphenyl boronic acid, an amine, and a diol to self-assemble diastereomeric iminoboronate ester (IBE) complexes whose ratio can be used to measure the ee's of amine and diol analytes using 1H and 19F NMR spectroscopic analysis. Examples where this supramolecular IBE assembly approach has been adapted to determine the ee of a range of analytes using other analytical techniques such as circular dichroism, fluorescence, and electrochemistry that are potentially applicable to high-throughput ee analysis are also discussed. Selected examples where this orthogonal self-assembly process has been used as a platform technology to construct boracyles, chiral auxiliaries/ligands, synthesise intelligent polymers/hydrogels, and prepare labelled peptides/proteins/biomolecules are also discussed.