Synthesis of 4,6,8-Trisubstituted Methyl Azulene-2-carboxylates

It is shown that sodium (methoxycarbonyl)cyclopentadienide ( 1 ), which is easily accessible from sodium cyclopentadienide and dimethyl carbonate in THF, reacts with 2,4,6-trisubstituted pyrylium tetrafluoroborates 2a–d in boiling MeOH to afford the corresponding methyl azulene-2-carboxylates 4a–d in good yields. The corresponding 1-carboxylates 3 were not found (cf. Schemes 1 and 2).