Dimethoxyethane is a reliable solvent for the synthesis of monosubstituted derivatives of o-carborane. The reaction of o-carborane with 1 equiv of BuLi and the appropriate electrophile in dimethoxyethane yields the desired monosubstituted derivative. The 1,2-Li-2-1,2-C2B10H10 compound is most probably avoided due to the bulkiness of the first Li(dimethoxyethane) substituent (see diagram), blocking attack by a second Li(dimethoxyethane) group. The method encounters problems if C,C’ thermodynamically stable rings can be formed.