A regioselective functionalization of cinnolines in positions 3 and 8 using metalations has been developed. This involves either the use of a frustrated Lewis pair consisting of BF3· Et2O and TMP2Mg· 2LiCl or the in situ generated base TMP2Zn· 2MgCl2· 2LiCl. Successive metalations allow the preparation of 3, 8-disubstituted cinnolines. Various functionalizations by acylation, allylation, and cross-coupling reactions with aryl halides or alkenyl iodides ...
