Periodinane
Periodinanes are chemical compounds containing hypervalent iodine. These iodine compounds are hypervalent because the iodine atom in it contains more than the 8 electrons in the valence shell required for the octet rule. When iodine is complexed with a monodentate electronegative ligand such as chlorine, iodine compounds occur with a +3 oxidation number as iodine(III) or λ3-iodanes or as a +5 oxidation number as iodine(V) or λ5-iodanes. Iodine itself contains 7 valence electrons and in a λ3-iodane three more are donated by the ligands making it a decet structure. λ5-iodanes are dodecet molecules. In an ordinary iodine compound such as iodobenzene the number of valence electrons is eight as expected. In order to get from iodine to a hypervalent iodine compound it gets oxidized with removal of first 3 electrons and then 5 electrons. The ligands in turn contribute electrons pairs and form coordinate covalent bonds by adding a total of 6 or 10 electrons back to iodine. In the L-I-N notation L stand for the number of electrons donated by ligands and N the number of ligands.
Periodinane compounds
The concept of hypervalent iodine was developed by J.J. Musher in 1969. In order to accommodate the excess of electrons in hypervalent compounds the 3-center-4-electron bond was introduced in analogy with the 3-center-2-electron bond observed in electron deficient compounds. One such bond exists in iodine(III) compounds and two such bonds reside in iodine(V) compounds.
The first hypervalent iodine compound, dichloroiodobenzene (C6H5Cl2I) was prepared in 1886 by the German chemist C. Willgerodt [1] by passing chlorine gas through iodobenzene in a cooled solution of chloroform.
- C6H5I + ICl3 → C6H5ICl2 + ICl
λ3-iodanes such as diarylchloroiodanes have a pseudotrigonal bipyramidal geometry displaying apicophilicity with a phenyl group and a chlorine group at the apical positions and other phenyl group with two lone pair electrons in the equatorial positions. The λ5-iodanes such as the Dess-Martin periodinane have square pyramidal geometries with 4 heteroatoms in basal positions and one apical phenyl group.
Classical organic procedures exist for the preparation of iodosobenzene diacetate from peracetic acid and acetic acid [2].
- C6H5I + CH3COOOH → C6H5I(OOCCH3)2
Phenyliodine bis(trifluoroacetate) or PIFA is a related compound based on trifluoroacetic acid
The acetate can be hydrolysed with water to iodoxybenzene or iodylbenzene C6H5O2I [3]
This compound was first prepared by Willgerodt by disproportionation of iodosylbenzene under steam distillation to iodylbenzene and iodobenzene
- 2 PhIO → PhIO2 + PhI
is a known oxidizing agent. Iodosobenzene diacetate can also be hydrolyzed to iodosylbenzene with sodium hydroxide which is actually a polymer with the molecular formula (C6H5OI)n [4]. Iodosylbenzene is used in organic oxidations. Dess-Martin periodinane (1983) is another powerful oxidant and an improvement of the IBX acid already in existence in 1893. The IBX acid is prepared from 2-iodobenzoic acid and potassium bromate and sulfuric acid [5] and is insoluble in most solvents whereas the Dess-Martin reagent prepared from reaction of the IBX acid with acetic anhydride is very soluble. The oxidation mechanism ordinarily consists of a ligand exchange reaction followed by a reductive elimination.
Periodinane uses
The predominant use of hypervalent iodine compounds is that of oxidizing reagent replacing many toxic reagents based on heavy metals [6].
Current research focuses on their use in carbon-carbon and carbon-heteroatom bond forming reactions. In one study such reaction, an intramolecular C-N coupling of an alkoxyhydroxylamine to its anisole group is accomplished with a catalytic amount of aryliodide in trifluoroethanol [7]:
In this reaction the periodinane (depicted as intermediate A) is formed by oxidation of the aryliodide with the sacrificial catalyst mCPBA which in turn converts the hydroxylamine group to a nitrenium ion B. This ion is the electrophile in ipso addition to the aromatic ring forming a lactam with a enone group.
References
- ↑ C. Willgerodt, Tageblatt der 58. Vers. deutscher Naturforscher u. Aertzte, Strassburg 1885.
- ↑ Template:OrgSynth
- ↑ Template:OrgSynth
- ↑ Template:OrgSynth
- ↑ Template:OrgSynth
- ↑ Hypervalent iodine(V) reagents in organic synthesis Uladzimir Ladziata and Viktor V. Zhdankin Arkivoc 05-1784CR pp 26-58 2006 Article
- ↑ First hypervalent iodine(III)-catalyzed C–N bond forming reaction: catalytic spirocyclization of amides to N-fused spirolactams Toshifumi Dohi, Akinobu Maruyama, Yutaka Minamitsuji, Naoko Takenaga and Yasuyuki Kita Chem. Commun., 2007, 1224 - 1226, doi:10.1039/b616510a