The First Generation of Azulenyl-Lithium and -Magnesium: A Novel, Versatile Method of Introducing a Substituent at the 2-Position of an Azulene Skeleton

1,3-Dihaloazulenes were effectively transformed into 2-substituted azulenes through lithiation at the 2-position by proton abstraction. Furthermore, 1,3-dichloro-2-iodoazulene was found to undergo iodine-lithium and -magnesium exchange to generate the corresponding azulenyl-lithium and -magnesium, respectively.