Comparative Reactivity of Hypervalent Iodine Oxidants in Metalloporphyrin‐Catalyzed Oxygenation of Hydrocarbons: Iodosylbenzene Sulfate and 2‐Iodylbenzoic Acid Ester as Safe and Convenient Alternatives to Iodosylbenzene

Abstract

A comparative study of the reactivity of 2-iodylbenzoic acid isopropyl ester (IBX-ester), oligomeric iodosylbenzene sulfate [(PhIO) 3 ·SO 3 ] n , and iodosylbenzene in the oxygenation of anthracene in the presence of metal porphyrin or phthalocyanine complexes is reported. Results of this study demonstrate that oligomeric iodosylbenzene sulfate and the IBX-ester are the most reactive oxygenating reagents that can be used as a safe and convenient alternative to the thermally unstable and potentially explosive iodosylbenzene.

Preparation and Reactivity of Polystyrene-Supported Iodosylbenzene: Convenient Recyclable Oxidizing Reagent and Catalyst

“…Interestingly, the PS-ISB/BF 3 ·OEt 2 system can oxidize anthracene to anthraquinone in good yield (Table 1, entry 14), while in the absence of BF 3 ·OEt 2 , using catalytic amount of binuclear iron(III) phthalocyanine(m-oxodimer), 11 anthracene can be oxidized only in low yield (8-9%) after long time (72 h, entry 15).…”

“…As expected, reactivity of PS-ISB in the BF 3 ·OEt 2 -catalyzed oxidation of alcohols is similar to (PhIO) n , and the polymer-supported reagent 2 can be used for efficient oxidation of various alcohols 5 to the corresponding carbonyl compounds 6 under mild conditions. Benzylic alcohols are oxidized to the corresponding aldehydes with 100% conversion after 1.5-12 hours except 4-methoxylbenzyl alcohol ( [8][9][10][11][12][13] were selectively oxidized to the respective ketones in good yields.…”

Synthesis and Properties of FeIII N=MnIV Heterometallic Complex with Tetra-tert-butylphthalocyanine Ligands

“…The progress in synthesis and characterization of latter compounds was recently reviewed by Ercolani an co-workers. [6] The studies of iron phthalocyanines as catalysts for oxidation processes showed that FePc in µ-oxo dimeric form in several cases exhibited better catalytic properties (activity and selectivity) than mononuclear FePc when using tert-butylhydroperoxide [7,8] and hypervalent iodine compounds [9,10] as oxidants. The high catalytic activity of µ-oxo dimeric complexes was unexpected since they are generally considered as catalytically inert species.…”

Halogens

“…A substantial improvement in this basis set has been reported (r-6-311G) which reduces the contraction error to 9.5 kcal/mol comparable to the other fourth row p-block elements. It is has been demonstrated that 79 Br NMR spectroscopy may be a practical tool for kinetic analysis. 27 This technique has the advantage of using d-orbitals as polarization functions in the basis set.…”