Structural and functional studies of boronic acid-diol recognition motifs

CARB 19

Eric V. Anslyn, anslyn@ccwf.cc.utexas.edu, Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station, A5300, Austin, TX 78712-0165
Boronic-acids are well known functional groups for the molecular recognition of diol containing structures. We have undertaken a structural study of o-(pyrrolidinylmethyl)phenylboronic acid and its complexes with bifunctional substrates such as catechol, a-hydroxyisobutyric acid, and hydrobenzoin in detail by x-ray crystallography, 11B NMR, and computational analysis. Our study predicts that the formation of an N-B dative bond, and/or solvolysis to afford a tetrahedral boronate anion, depends on the solvent and the complexing substrate present. Specifically, from 11B NMR studies, complexation with electron withdrawing and/or vicinally bifunctionalized substrates promotes both the formation of N-B dative bonds and the solvation of sp2 boron to a tetrahedral sp3 boronate. The conclusion has assisted us in the design of chemosensing technologies based on o-(N,N-dialkylaminomethyl)arylboronate scaffolds. In that regard, we have extensively used boronic acids in molecular recognition schemes for sensing the chirality of diol-containing structures using colorimetric methods. Both the structural analysis and the assay for enantiomeric excess will be discussed in this presentation.