Superacid-Catalyzed Electrophilic Formylation of Adamantane with Carbon Monoxide Competing with Koch-Haaf Carboxylation

Article abstract of DOI:10.1021/ja00211a027

The superacid-catalyzed reaction of adamantane with carbon monoxide was investigated. 1-Adamantanecarboxaldehyde together with 1-adamantaneecarboxylic acid and 1-adamantanol (the products of the reaction of intermediate 1-adamantyl cation) was obtained.The mechanism of the formation of 1-adamantanecarboxaldehyde by electrophilic formylation involving ?-insertion of the formyl cation is indicated.This is contrasted by the competing protolytic ionization of adamantane to 1-adamantyl cation which gives with CO 1-adamantanoyl cation and subsequently 1-adamantanecarboxylic acid (Koch-Haaf reaction) or by hydrolysis 1-adamantanol.