The reaction of (2-aminobenzyl) triphenylphosphonium bromide with aromatic aldehydes or α,β-unsaturated aldehydes under microwave-assisted conditions constitutes a new synthesis of 2-substituted indoles in high yields (81−97%) in a one-pot reaction. The adduct from indole-4-carboxaldehyde was an advanced intermediate in the synthesis of arcyriacyanin A.