Nucleophilic substitution in dibenz[b,d]iodolium and 11,12-dihydro-10H-dibenz[b,g]iodocinium cations

Cyclic diaryliodonium ions: old mysteries solved and new applications envisaged

“…As early as 1956, Sandin and co-workers 7 reported that the condensation of iodosyl compounds with arenes to give linear † Dedicated to the memory of Dr Aleksandr Nikolaevich Vanchikov (1952Vanchikov ( -1998 iodonium cations, can furnish cyclic iodonium salts if conducted intramolecularly (eqn. ( 2)).…”

“…This strategy has since been successfully used for the synthesis of 1, 8-11 2, 8,12,13 3, 14 and 4 9 with various counterions and a wide variety of other iodonium heterocycles, e.g., 5-10. 12,[15][16][17][18][19][20][21] The synthesis is conveniently carried out as a onepot, two-step process.…”

“…In addition to the wellknown methods for preparing iodonium tertrafluoroborates, such as extraction, precipitation, and the reactions of a corresponding halide with [Et 3 O] + BF 4 2 or AgBF 4 , 1-4 an elegant new technique has been recently developed. 9 This technique is exemplified by the preparation of [4]BF 4 from the reaction solution containing cation 4 (eqn. ( 2)).…”

“…( 8)). 9 The readily soluble chromium complex is effortlessly removed from the iodonium tetrafluoroborate by washing with cold water.…”

Computational investigation of cyclic substituted iodine(III) halogen bond donors

“…We thus compared cyclic iodine(III) compounds with different bridging groups, going from no bridging group (1H) to a bridging propylene unit (10CH2, 10(CH2)2, 10(CH2)3) in Figure 14. 13,14 Unsurprisingly, the barrier to reductive elimination rapidly decreases with the number of methylene units, as the more flexible geometry reduces the distortion required for the reductive elimination. The Lewis acidity and electron affinity are also decreased by adding bridging methylene units.…”