A convenient synthesis of α-diones and their monoprotected acetals, ie α-ketoacetals, was developed by mercury induced solvolysis of regiospecifically formed α-chloro-α-(alkylthio) ketones. Analogously, α-alkoxy-α-sulfenylated ketones were formed when reacting α-chloro- α-sulfenylated ketones with an alkaline alcoholic medium. α-Alkoxy-α-sulfenylated ketones themselves could be transformed into α-diones or α-ketoacetals, which in turn were ...