ChemInform Abstract: COMPETITIVE BINDING OF PERCHLORATE AND TRIFLUOROMETHANESULFONATE ANIONS IN REACTIONS OF ARYLIODOSO DERIVATIVES WITH OLEFINS

Organic Polyvalent Iodine Compounds

“…The first step in this mechanism involves electrophilic anti -addition of the reagent to the double bond, and the second step is nucleophilic substitution of the iodonium fragment by tosylate anion with inversion of configuration. Such a polar mechanism also explains the skeletal rearrangements in the reactions of HTIB with polycyclic alkenes, participation of external nucleophiles, and the intramolecular participation of a nucleophilic functional group with the formation of lactones and other cyclic products. − Analogous reactivity pattern is also typical of [hydroxy[(methylsulfonyl)oxy]iodo]benzene …”

“…For example, 1-hexene reacts with BTI in the presence of LiClO 4 or LiOTf to produce diperchlorate or -triflate esters of 1,2-hexanediol. 167 Merkushev and co-workers have found that alkynes can be oxidized with BTI to afford the respective 1,2diones in excellent yields. [168][169][170] In some cases, this reaction is accompanied by a complete triple-bond cleavage with the formation of carboxylic acids.…”

“…The analogous reaction of alkenes with DIB or BTI in the presence of external nucleophiles affords the respective derivatives of 1,2-diols. For example, 1-hexene reacts with BTI in the presence of LiClO 4 or LiOTf to produce diperchlorate or -triflate esters of 1,2-hexanediol …”