A Lewis Base–Silyl Lewis Acid Cooperative Catalyst for the Iodochlorination of Tetrasubstituted Alkenes

Abstract We have developed a Lewis base‐silyl Lewis acid cooperative catalyst for the iodochlorination of alkenes. In the presence of 10–20 mol% of Ph 3 P=O, the iodochlorination of tetrasubstituted alkenes with N ‐iodosuccinimide and tert ‐butyldimethylchlorosilane proceeded efficiently at −40 °C to provide the corresponding 1,2‐iodochloroalkanes that cannot be easily obtained via conventional methods. A series of 31 P NMR experiments suggests that the cooperative activation of the reaction components facilitates the generation of the active iodochlorinating species.