Studies on the Reactions of Thiocarbonyl S‐Methanides with Hetaryl Thioketones

Abstract Dihetaryl thioketones react with thiocarbonyl ylides to give 1,3‐dithiolanes in high yields. No competitive side reactions of the thiocarbonyl ylides were observed, evidencing the ‘superdipolarophilic’ character of this less‐known group of thioketones. Depending on the type of substituents present in both the thiocarbonyl ylide and the thioketone, formal [3+2] cycloadditions occur with complete regioselectivity or with formation of a mixture of both regioisomers. Regioselective formation of the sterically more crowded 1,3‐dithiolanes is explained via a mechanism involving stabilized 1,5‐biradicals. In systems with less‐efficient radical stabilization, e.g., in the case of adamantanethione S‐methanide, substantial violation of the regioselectivity was observed as a result of steric hindrance.