New Frontiers in Organosodium Chemistry as Sustainable Alternatives to Organolithium Reagents

Abstract

With their highly reactive respective C−Na and N−Na bonds, organosodium and sodium amide reagents could be viewed as obvious replacements or even superior reagents to the popular, widely utilised organolithiums. However, they have seen very limited applications in synthesis due mainly to poor solubility in common solvents and their limited stability. That notwithstanding in recent years there has been a surge of interest in bringing these sustainable metal reagents into the forefront of organometallics in synthesis. Showcasing the growth in utilisation of organosodium complexes within several areas of synthetic chemistry, this Minireview discusses promising new methods that have been recently reported with the goal of taming these powerful reagents. Special emphasis is placed on coordination and aggregation effects in these reagents which can impart profound changes in their solubility and reactivity. Differences in observed reactivity between more nucleophilic aryl and alkyl sodium reagents and the less nucleophilic but highly basic sodium amides are discussed along with current mechanistic understanding of their reactivities. Overall, this review aims to inspire growth in this exciting field of research to allow for the integration of organosodium complexes within common important synthetic transformations.

Distance-Independent Efficiency of Triplet Energy Transfer from π-Conjugated Organic Ligands to Lanthanide-Doped Nanoparticles

“…We hypothesize that the deprotonated BPEA derivatives have larger binding affinities for the highly electropositive Nd 3+ ions than for the Na + ions. This is in line with lanthanides being some of the most oxophilic elements in the periodic table and exhibiting higher oxophilicity than the alkali metals including sodium. , The preferential binding ensures close coupling between the energy donating organic molecules and energy accepting lanthanide ions in the LnNPs.…”

“…This is in line with lanthanides being some of the most oxophilic elements in the periodic table and exhibiting higher oxophilicity than the alkali metals including sodium. 36,37 The preferential binding ensures close coupling between the energy donating organic molecules and energy accepting lanthanide ions in the LnNPs.…”

Synthesis, characterisation, and catalytic application of a soluble molecular carrier of sodium hydride activated by a substituted 4-(dimethylamino)pyridine

“…Remarkably, onward reactivity of intermediate organosodium compounds has even been achieved in reaction mixtures containing protic substances such as water, glycerol, deep eutectic solvents (DESs) or air, all generally nemeses of polar organometallic compounds 18 . A selection of these and other recent advances has been captured in a mini review 19 .…”

Dual Basicity and Nucleophilicity of Organosodium Reagents in Benzylic C−H Additions of Toluenes to Diarylethenes and Ketones

“…In parallel to these studies, within polar organometallic chemistry there has been a renaissance on applications of organosodium reagents in organic synthesis [10a,b] . Studies by the groups of Asako and Takai have shown the potential of using Na dispersions to generate arylsodium species in situ that can subsequently be functionalised via Pd catalysed cross‐coupling reactions [11a,b] .…”