ChemInform Abstract: Reactions of [Fluoro(methylsulfonyloxy)iodo]benzene. Part 2. Reaction of [Fluoro(sulfonyloxy)iodo]benzene with Acyclic Olefins.

Abstract

Reactions of [Fluoro(methylsulfonyloxy)iodo]benzene. Part 2. Reaction of [Fluoro(sulfonyloxy)iodo]benzene with Acyclic Olefins.-Title compounds (II) undergo an electrophilic addition reaction to acrylate (I) in the presence of the corresponding lithium sulfonates to give regioisomeric fluoro(sulfonyloxy) derivatives (III) and (IV). In the case of 1-hexene (V), 1,2-disulfonate (VI) is formed (yield not given). An analogous product is isolated from the reaction with 1-heptene. -(PIRKULIEV, N. SH.; BREL, V. K.; AKHMEDOV, N. G.; MAGERRAMOV, A. M.; SHYKHALIEV, N. G.; ZEFIROV, N. S.; Russ.

Synthesis, structural characterization, reactivity and catalytic activity of mixed halo/triflate ArI(OTf)(X) species

“…They later reported a compound of the same family with the phenyl group being a p-diiodobenzene which displayed analogous reactivity, but again it was only proposed as an intermediate at low temperatures based on the reactant and products and could not be observed. During this period, the methanesulfonate (oMS) analogue in PhIF(oMS) was also reported, [17][18][19] and displayed analogous reactivity to PhIF(OTf). Again, this compound was not subject to characterization.…”

“…Again, this compound was not subject to characterization. Subsequent to these initial reports, PhIF(OTf) and PhIF(oMS) have been used in synthetic applications several times by Zefirov including reactions with norbornene, 19 cyclic & acyclic olefins 18,20 and as a pathway to Weiss' reagents. [21][22][23] Stang's first report mentions that PhIF(OTf) formed a [Ph-I-Ph-I] + [OTf]on exposure to iodobenzene, 16 demonstrating that PhIF(OTf) decomposes via an EAS pathway to form this iodonium salt, explaining why PhIF(oMS) and PhIF(OTf) were never characterized.…”

Synthesis, structural characterization, reactivity and catalytic activity of mixed halo/triflate ArI(OTf)(X) species

“…They later reported a compound of the same family with the phenyl group being a p-diiodobenzene which displayed analogous reactivity, but again it was only proposed as an intermediate at low temperatures based on the reactant and products and could not be observed. 18 During this period, the methanesulfo-nate (OMs) analogue in PhIF(OMs) was also reported, [19][20][21] and displayed analogous reactivity to PhIF(OTf ). Again, this compound was not subject to characterization.…”

“…Subsequent to these initial reports, PhIF(OTf ) and PhIF(OMs) have been used in synthetic applications several times by Zefirov including reactions with norbornene, 21 cyclic & acyclic olefins 20,22 and as a pathway to Weiss' reagents. [23][24][25] Stang's first report mentions that PhIF(OTf ) formed a [Ph-I-Ph-I] + [OTf ] − on exposure to iodobenzene, 17 demonstrating that PhIF(OTf ) decomposes via an EAS pathway to form this iodonium salt, explaining why PhIF(OMs) and PhIF(OTf ) were never characterized.…”