Electrostatic and stereoelectronic interaction impacts on the structural properties and isomerization reactions of methyl isocyanide and its trihalo-analogs

Asmic: An Exceptional Building Block for Isocyanide Alkylations

“…Surmising that the lithiated isocyanide might exhibit carbene character, several metal chelators were added (HMPA, 18-crown-6, LiCl, DMPU, DME, KOt-Bu, and TMEDA) in an attempt to suppress the rearrangement . Among these, the introduction of TMEDA to a −78 °C THF solution of 13 before the addition of BuLi was found to afford only isocyanide 15a , completely suppressing the formation of the nitrile 14a …”