Hydroiodination‐Triggered Cascade Reaction with I2/PPh3/H2O: Metal‐Free Access to 3‐Substituted Phthalides from 2‐Alkynylbenzoates

Phthalide is an important scaffold found in several biologically active compounds. Therefore, effective methods for the synthesis of phthalides are strongly desired. Herein, we describe the metal‐free synthesis of 3‐substituted phthalides by the reductive hydroiodination of 2‐alkynylbenzoates through an I 2 /PPh 3 /H 2 O‐triggered cascade reaction. A variety of 3‐substituted phthalides were synthesized in excellent yields by a one‐pot reaction involving four processes: desilylation, hydroiodination, cyclization, and reduction.