Abstract

The in situ monitoring of dynamic covalent macromolecular boronate esters represents a difficult task. In this report, we present an in situ method using fluoride coordination and 11B NMR spectroscopy to determine the amount of boronate esters in a mixture of boronic acids and cis-diols. With fluoride coordination, the boronic acid and boronate esters afforded trifluoroborate and fluoroboronate esters, giving identical resonances at 3 and 9 ppm in the 11B NMR spectra. The same titration did not alter the resonance of amine-coordinated boronate esters, which gave resonances of 14 ppm in the 11B NMR spectra. Therefore, boronic acids, boronate esters, and amine-coordinated boronate esters gave three identical resonances, and the ratio of each component was obtained by deconvolution for a further equilibrium analysis. This method monitored the conversion among three species in various conditions, including separation. Accordingly, boronate esters were more stable after precipitation than chromatography, in which 29% and 20% of boronate esters were lost after purification. This method was applied to study the reaction between the boronic acid-decorated defect lysine dendron (16) and dopamine. No boronic acid signal was observed after adding 1 equivalent of dopamine; no boronic acid signal was observed in the NMR spectrum. According to the spectrum, the product contains 65% boronate ester and 35% N–B-coordinated derivatives. This method helps identify the presence of the three intermediates and provides more insights into this reaction.

Talk to us

Join us for a 30 min session where you can share your feedback and ask us any queries you have

Schedule a call

Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.