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Updated: Dec 4, 2025

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
Tandem Mn-I Exchange and Homocoupling Processes Mediated by a Synergistically Operative Lithium Manganate
Marina Uzelac1, Pasquale Mastropierro2, Marco de Tullio3
1EastCHEM School of Chemistry, University of Edinburgh, Edinburgh, EH9 3FJ, UK.
Abstract:
Pairing lithium and manganese(II) to form lithium manganate [Li2 Mn(CH2 SiMe3 )4 ] enables the efficient direct Mn-I exchange of aryliodides, affording transient (aryl)lithium manganate intermediates which in turn undergo spontaneous C-C homocoupling at room temperature to furnish symmetrical (bis)aryls in good yields under mild reaction conditions. The combination of EPR with X-ray crystallographic studies has revealed the mixed Li/Mn constitution of the organometallic intermediates involved in these reactions, including the homocoupling step which had previously been thought to occur via a single-metal Mn aryl species. These studies show Li and Mn working together in a synergistic manner to facilitate both the Mn-I exchange and the C-C bond-forming steps. Both steps are carefully synchronized, with the concomitant generation of the alkyliodide ICH2 SiMe3 during the Mn-I exchange being essential to the aryl homocoupling process, wherein it serves as an in situ generated oxidant.
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