On the Configurational Stability of Chiral, Nonracemic Fluoro‐ and Iodo‐[D₁]Methyllithiums

Abstract

Enantiomerically pure fluoro-[D1]methyllithium and iodo-[D1]methyllithiums of up to 92% ee were generated by transmetalation of the corresponding stannanes with MeLi in THF at various temperatures. The intermediate halo-[D1]methyllithiums were trapped with benzaldehyde or acetophenone already present in excess in the reaction mixture to either give halohydrins or to disintegrate to carbene. The fluoro-[D1]methyllithiums were found to be microscopically configurationally stable within the tested range of -95 to 0 °C, but chemically only stable at temperatures below -95 °C due to a rapidly increasing portion disintegrating to carbene. The iodo-[D1]methyllithiums were configurationally labile relative to the rate of addition to PhCHO at all temperatures tested (-95 to -30 °C). Disintegration to carbene interfered as well.