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Boronic ester functionalised 1,8-diboryl-naphthalene scaffolds: fluoride versus oxide chelation
Anna C Booth1, Petra Vasko2, M Ángeles Fuentes1
1Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK. simon.aldridge@chem.ox.ac.uk.
None:
1,8-Bis(boronic ester) derivatives of naphthalene, 1,8-C10H6{B(OR)2}2, present an attractive target as receptors for the fluoride ion via B-F-B chelation, but are synthetically challenging to access due to the competing formation of a very stable anhydride containing a B-O-B motif. By contrast, unsymmetrical systems of the type 1,8-C10H6{B(OR)2}(BR'2) can be synthesized for (OR)2 = 1,2-O2C6H4 (i.e. Cat) and R' = Mes. This system is shown to be competent for the uptake of F-, making use of a chelating mode of action and the formation of a bridging B-F-B motif between the two boron centres. However, both experimental and quantum chemical studies indicate that the micro2-F adduct is the kinetic product of fluoride uptake, with an alternative structural motif featuring a terminal B-F bond and a B-O-B bridge using one of the catechol oxygens being (marginally) more favourable thermodynamically.
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