The generally accepted monoacyloxyboron mechanism of boron-catalysed direct amidation is brought into question in this study, and new alternatives are proposed.

The study of boron-mediated reactions in organic synthesis and reactions of organoboron compounds is greatly facilitated by the use of B NMR. However, the identification and characterization of reaction intermediates in often complex systems is far from trivial, asB NMR does not provide any detailed structural information. Greater insight into the structures present in such systems can be obtained by using DFT chemical shift calculations to support or exclude proposed reaction intermediates. In this article, we report a rapid and accessible approach to the calculation of B NMR shifts that is applicable to a wide range of organoboron compounds.

Interactions between hindered Lewis acids and Lewis bases result in well-known frustrated Lewis pair behavior. Recent research has tended to concentrate on very hindered systems, resulting in high levels of activation, but not necessarily reactivity. In this article, we review the state-of-the-art and try to identify how FLP chemistry may develop further to give a wider range of applicable catalytic reactions, i.e. through softening both Lewis acid and base strengths, reducing hindrance and by controlling associative processes through tether length and dynamic effects.

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