Direct Assembly of Benzo[e]indoles by Diels–Alder Reaction of Arynes and 2‐Vinylpyrroles

A direct synthetic strategy for the construction of benzo[ e ]indoles by Diels–Alder reaction of 2‐vinylpyrroles and arynes was developed. By introducing CHPh 2 as the N ‐protecting group, the arynes selectively reacted with the external vinyl group instead of the pyrrole ring itself. A series of substituted benzo[ e ]indoles were afforded with high selectivity in good yields.