Novel superelectrophilic complexes for low-temperature alkane and cycloalkane transformations

Abstract

The results of studies on the elaboration of new superelectrophilic complexes and their use for efficient low-temperature transformations of alkanes and cyeloalkanes, such as cracking, isomerization, alkylation, and single-step functionalization (acytation, carbonylation, ionic monobromination, sulfilrization, thioacylation, etc.), are summarized. The activity of new aprotic organic and inorganic superacids is compared to that of known electrophilic systems, including protic superacids. The reasons for the superelectrophilic properties of new active systems are considered.

Superacid‐Catalyzed Reactions

“…Two alternative mechanisms have been suggested. Furthermore, the same catalysts could be The superelectrophilic AcBr-nAlBr 3 complexes, called aprotic organic superacids developed by Vol'pin and co-workers, 119,120 were used in the isomerization of C 12 H 20 tricyclanes with the main component being perhydroacenaphthene to dimethyl-and ethyladamantanes 121 Two mechanistic schemes (Schemes 5.14 and 5.15) via carbocationic intermediates have been proposed by Paquette and Balogh. (ii) n-Butane is protonated by the Brønsted acid to form a carbonium ion intermediate; and either the hydrogen formed is used up to reduce SbF 5 or it loosely remains bound to the ion during the isomerization process.…”