ChemInform Abstract: GaCl₃‐ and TiCl₄‐Catalyzed Insertion of Isocyanides into a C—S Bond of Dithioacetals.

Abstract

Thio compounds Q 0590GaCl3-and TiCl4-Catalyzed Insertion of Isocyanides into a C-S Bond of Dithioacetals. -Dithioacetals (I) require slow addition of isocyanide (II) to avoid formation of double-insertion products. Comparable yields are obtained with GaCl3 and TiCl4. Substrates (IV) bearing aromatic substituents afford exclusively mono-insertion products, even if the isocyanide is added all at once. The same effect is observed for mixed O,S-acetals (VI), where the insertion occurs only at the C-S bond. The thioimidates can be hydrolyzed under acidic conditions into thioesters as useful building blocks for organosulfur compounds. -(TOBISU, M.; ITO, S.; KITAJIMA, A.; CHATANI*, N.; Org. Lett. 10 (2008) 22, 5223-5225; Dep. Appl. Chem., Fac. Eng., Osaka Univ., Suita, Osaka 565, Japan; Eng.) -R. Simon 15-084