Ultrastabilized boranes : a study into the synthesis, structure and reactivities of heterosubstituted organoboranes.

Abstract

Three heterosubstituted boranes were successfully synthesized from the corresponding amines and borane dimethyl sulfide (BH3·DMS) in high yields, and were noted to be significantly more stable than the analogous dioxo-compounds. In situ 11B NMR spectroscopy indicated that the mechanism of the reaction to form these boranes contains two intermediates and supports a step-wise addition mechanism. 15N NMR spectroscopic analysis of the boranes identified a downfield shift in the location of the nitrogen signal from the typical amine region towards the aromatic region, supporting the theory of electron back-donation from the nitrogen lone pair to the boron atom’s vacant pz-orbital. The three boranes proved to be suitable hydroboration reagents under microwave-assisted conditions, with Wilkinson’s catalyst and a rhodium(I) carbonyl hydride catalyst both showing catalytic ability, however yields were noted to be dependent on the borane, the olefin and the catalyst. Twelve heterosubstituted boranes were successfully synthesized in high yields as products from condensation reactions between diamines and boronic acids both in solution and under microwave-assisted solvent-free conditions, which resulted in the reaction time being reduced from three hours to 15 minutes. 15N NMR spectroscopic analysis of these compounds showed a similar downfield shift in the amine signal as was observed previously, lending support to the electron back-donation explanation for the stability of these compounds. Crystals suitable for X-Ray diffraction analysis were grown for four 1,8-diaminonaphthalene-based boranes, and analysis of the data showed that the compounds are not planar as originally thought, rather there is a degree of torsion inherent in each of the structures, ranging from a slight (3-4%) to a substantial deviation (19-20%). It was shown that heterosubstituted boranes can be used in Petasis reactions as the organoborane reagent in a number of cases, although the reaction conditions used were not optimized for these compounds. Microwave irradiation was also successfully employed in the Petasis reactions, which reduced the reaction time from 48 hours to 10 minutes.