Nucleophilic alkaline earth boryls: from conception and theory to application

This EPSRC funded project is in collaboration with Prof. Mike Hill and Dr Alex Cresswell, who are both at the University of Bath. Dr Sam Neale is the computational post-doctoral research associate working with me on this project.

We are building on our discovery (Nature Commun. 2017, 8, 15022) that derivatives where boron is bonded to a less electronegative group 2 element, e.g. magnesium, are easily generated by activation of B-B bonds of commercially available diboranes. In contrast to the vast majority of available boron reagents, the boron in these compounds reacts as a potent electron donor (nucleophile), providing the potential to allow the synthesis of a wide variety of new boron-containing molecules. In this project, we are applying a multifaceted inorganic/organic synthetic and computational approach to devise, understand and apply a wide array of new and highly reactive boron derivatives of the group 2 metals, primarily magnesium and calcium. The attractiveness of these latter elements is underscored by their negligible toxicity, high natural abundance and resultant low cost. Furthermore, the boron nucleophiles developed in this project will be used in the synthesis of a plethora of unprecedented and previously inaccessible organic and inorganic boron-containing compounds. Our ultimate objective is to ensure that these reagents are available from commercial chemical suppliers and nothing short of establishing previously inaccessible boron nucleophiles as off-the-shelf reagents in the synthetic chemist's larder.

Recent Publications:

  • Oxygen Atom Transfer and P(V) Reduction by Heterolytic Diborane Activation (2019); DOI: 10.1039/C9CC04294F

  • Snapshots of Magnesium-Centred Diborane Heterolysis by an Outer Sphere SN2 Process (2019); DOI: 10.1039/C9SC02087J

  • Magnesium-Mediated Nucleophilic Borylation of Carbonyl Electrophiles (2018); DOI: 10.1021/acs.organomet.8b00408