Reactions of a Dilithiomethane with CO and N2 O: An Avenue to an Anionic Ketene and a Hexafunctionalized Benzene.

Synthesis of value-added products from simple C1 feedstocks is an attractive alternative avenue to traditional fossil fuels. Hexa-substituted benzene derivatives are highly useful molecules but are often challenging to prepare. Herein, we report that the lithium complex [(Ph2 P(S))2 CLi2 (THF)]2 1 reacts with CO lead to C-C bond formation and migration of a Ph2 P(S)-fragment affording 2. Subsequent reaction with N2 O results in oxidative cleavage of a P-C bond affording [Ph2 P(S)OLi(THF)2 ]2 4 and the anionic ketene-derivative Ph2 P(S)CCOLi(THF)2 5. Heating 5 prompts cyclotrimerization giving the hexa-substituted benzene derivative [Ph2 P(S)CCOLi(THF)2 ]3 6 regioselectively. This transition metal-free protocol to a hexa-substituted benzene is viable on a gram scale and permits the incorporation of 13 C labels. The mechanisms of these reactions are detailed via extensive DFT computations.