Palladium-Catalyzed Desilylative Acyloxylation of Silicon–Carbon Bonds on (Trimethylsilyl)arenes: Synthesis of Phenol Derivatives from Trimethylsilylarenes

A strategy for desilylative acetoxylation of (trimethylsilyl)­arenes has been developed in which (trimethylsilyl)­arenes are converted into acetoxyarenes. The direct acetoxylation is performed in the presence of 5 mol % of Pd­(OAc)₂ and PhI­(OCOCF₃)₂ (1.5 equiv) in AcOH at 80 °C for 17 h. The acetoxyarenes are obtained in good to high yields (67–98%). The synthetic utility is demonstrated with a one-pot transformation of (trimethylsilyl)­arenes to phenols by successive acetoxylation and hydrolysis. Furthermore, desilylative acyloxylation of 2-(trimethylsilyl)­naphthalene using several carboxylic acids has been conducted

Synthesis of 1,2-Bis(trimethylsilyl)benzene Derivatives from 1,2-Dichlorobenzenes Using a Hybrid Metal Mg/CuCl in the Presence of LiCl in 1,3-Dimethyl-2-imidazolidinone

A practical and safe synthesis of 1,2-bis­(trimethylsilyl)­benzene from 1,2-dichlorobenzene and Me3SiCl was achieved by use of a hybrid metal of Mg and CuCl in the presence of LiCl in 1,3-dimethyl-2-imidazolidinone (DMI). This method does not require a toxic HMPA, provides a high yield of the product under mild conditions, and is also applied to synthesis of substituted 1,2-bis­(trimethylsilyl)­benzenes and poly­(trimethylsilyl)­benzenes