Sodium in One-Step Processes

Although the number of applications of sodium in one-step processes is limited, some Na-Barbier reactions are worth mentioning here. 

The metal was the first to be generally applied in organic synthesis. In 1855, after initial attempts with potassium one year earlier [1], Adolphe Wurtz [2], reacted sodium with haloalkanes. This attempt to produce radicals was similar 

In 1864, Tollens together with Fittig [3], widened the scope of the Wurtz reaction by applying it to a mixture of aliphatic and aromatic organohahdes, thus introducing the Wurtz-Fittig reaction. 

One year later an unsuccessful attempt to couple two benzoyl groups (from benzoyl chloride) with sodium was reported [4]. This reaction was later carried out in 1883 [5]. 

In 1895, four years before Barbier s report [6] on the one-step synthesis with magnesium, sodium was used in a one-pot reaction with bromobenzene and ethyl oxalate, the unforeseen product being triphenylmethanol [7]. 

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Addition of an Electron Transfer Agent. In one of the earliest reports on Li-Barbier chemistry [49], a comparison was made of results obtained with lithium and with sodium in one-step processes. It was found that yields with sodium could be improved by the addition of an electron acceptor such as naphthalene or biphenyl in stoichiometric as well as in catalytic amounts. 

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