Sustainable I ₂ /H ₂ O ₂ ‐Driven Mechanochemical Thiolation of Cyclic Enamines

Herein, we report an environmentally benign and green mechanochemical protocol for the thiolation of cyclic enamines using a liquid‐assisted grinding approach. A broad range of cyclic enamines, including 2‐amino‐1,4‐naphthoquinones, 5‐aminoisoxazoles, and 6‐aminouracils, underwent efficient thiolation in the presence of I 2 (30 mol%) and H 2 O 2 (6 equiv.), affording the corresponding thio‐functionalized products in good yields within 30 min under grinding conditions. This sustainable methodology eliminates the need for metal catalysts, offering an eco‐friendly alternative to conventional synthetic strategies. All the synthesized compounds were fully characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, and high‐resolution mass spectrometry analyses. Additionally, the molecular structure of compound 3f was unambiguously established through single‐crystal X‐ray diffraction analysis.