Benzofused seven-membered heterocycles
such as 1,4-benzo[
e
]diazepines (1,4-BZDs) and 1,4-benzo[
e
]oxazepines (1,4-BZOs) were efficiently synthesized by
Rh-catalyzed
hydrofunctionalization of internal alkynes and allenes in good to
excellent yields. The asymmetric hydroamination of (aminomethyl)anilines
gave rise to 3-vinyl-1,4-BZDs with excellent enantioselectivities.
Orthogonal
N
-deprotection of 1,4-BZDs allowed an
easy entry to an advanced pyrrolobenzodiazepine metabolite of the
V
2
-receptor antagonist Lixivaptan.