Hypervalent Iodine Reagents

25 May, 2016 / by SK / in Reactions

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General Characteristics

Iodine can exist in high valence states because of its higher polarizability and smaller electronegativity compared with other halogen elements.

Hypervalent iodine compounds are readily reduced to stable monovalent state with the dissociation of apical groups, thus they act as good oxidizing agents.

Synthetically useful trivalent iodine reagents (λ³-iodane) include the following:

Pentavalent iodine (λ⁵-iodane) and higher valence states (such as iodine(VII)) are also known, among which the Dess-Martin reagent and periodate salt are commonly used as mild oxidizing agents.

General References

Valvoglis, A. Synthesis 1984, 709.
Stang, P. F.; Zhdankin, V. V. Chem. Rev. 1996, 96, 1123. DOI: 10.1021/cr940424+
Varvoglis, A.; Spyroudis, S. Synlett 1998, 221. DOI: 10.1055/s-1998-1619
Zhdankin, V. V.; Stang, P. J. Chem. Rev. 2002, 102, 2523. doi:10.1021/cr010003+
Moriarty, R. M. J. Org. Chem. 2005, 70, 2893. doi:10.1021/jo050117b
Wirth, T. Angew. Chem. Int. Ed. 2005, 44, 3656. DOI: 10.1002/anie.200500115
Deprez, N. R.; Sanford, M. S. Inorg. Chem. 2007, 46, 1924. doi:10.1021/ic0620337
Zhdankin, V. V. Chem. Rev. 2008, 108, 5299. doi:10.1021/cr800332c
Ochiai, M.; Miyamoto, K. Eur. J. Org. Chem. 2008, 4229. DOI: 10.1002/ejoc.200800416
Merritt, E. A.; Olofsson, B. Angew. Chem. Int. Ed. 2009, 48, 9052. DOI: 10.1002/anie.200904689
Dohi, T.; Kita, Y. Chem. Commun. 2009, 2073. DOI: 10.1039/b821747e
Uyanik, M.; Ishihara, K. Chem. Commun. 2009, 2086. DOI: 10.1039/b823399c

Reaction Mechanism

The reactivity of hypervalent iodine compounds generally increases with the degree of how easily the apical groups dissociate.

Examples

Asymmetric oxidation using a chiral hypervalent iodine reagent.^[1]

Progress has been made in recent years to reduce the amount of iodine reagents to substoichiometric.

Experimental Procedure
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References

(1) Dohi, T.; Maruyama, A.; Takenaga, N.; Senami, K.; Minamitsuji, Y.; Fujioka, H.; Carmmerer, S. B.; Kita, Y. Angew. Chem. Int.Ed. 2008, 47, 3787. doi:10.1002/anie.200800464