GaCl3- and TiCl4-Catalyzed Insertion of Isocyanides into a C-S Bond of Dithioacetals

The insertion reaction of isocyanide into a C-S bond of dithioacetals is catalyzed by GaCl3 or TiCl4 to afford thioimidates containing an alpha-alkylthio group. Balanced thiophilicity of these Lewis acids is critical for efficient catalysis.