Polymer-Supported Hypervalent Iodine as Green Oxidant in Organic Synthesis
14 September 2011 (online)
2-Iodoxy benzoic acid (IBX) and Dess-Martin periodinane (DMP, Scheme [¹] ) have been extensively employed in organic synthesis as mild and highly selective reagents for the oxidation of alcohols to carbonyl compounds as well as for a variety of other synthetically useful oxidative transformations. However, IBX and DMP are not perfect with respect to the principles of green chemistry since they are normally used as non-recyclable, stoichiometric reagents in non-recyclable organic solvents, which have potentially damaging environmental effects. [¹] [²] Reactions of monomeric hypervalent iodine reagents with organic substrates lead to the respective iodoarenes as byproducts, which in general are not recoverable from a reaction mixture. The discovery of recyclable reagents and catalytic systems based on the iodine redox chemistry has initiated a major surge of research activity and added a new dimension to the field of hypervalent iodine chemistry. Polymer-supported modifications of hypervalent iodine reagents retain the useful reactivity of their monomeric analogues with the added advantage of being readily recyclable and reusable. Numerous new organoiodine(V) reagents have recently been developed, and it is anticipated that these safe and efficient derivatives and analogues of IBX will find widespread synthetic application in the future.
Scheme 1 Preparation of IBX and DMP
AnastasPT. WarnerJC. Green Chemistry: Theory and Practice Oxford University Press Inc.; New York: 1998.
MülbaierM. GiannisA. Angew. Chem. Int. Ed. 2001, 40: 4393
SorgG. MengeiA. JungG. RademannJ. Angew. Chem. Int. Ed. 2001, 40: 4395
LeiZQ. MaHC. ZhangZ. YangYX. React. Funct. Polym. 2006, 66: 840
LeiZ. DeneckerC. JegasothyS. SherringtonDC. SlaterNKH. SutherlandAJ. Tetrahedron Lett. 2003, 44: 1635
BrombergL. ZhangH. HattonTA. Chem. Mater. 2008, 20: 2001
JangHS. ChungWJ. LeeYS. Tetrahedron Lett. 2007, 48: 3731
KumarA. MauryaRA. AhmadP. J. Comb. Chem. 2009, 11: 198
BerniniR. MincioneE. BarontiniM. CrisanteF. FabriziG. Tetrahedron Lett. 2009, 50: 1307
ChenJM. ZengXM. MiddletonK. ZhdankinVV. Tetrahedron Lett. 2011, 50: 1952
QianW. JinE. BaoW. ZhangY. Angew. Chem. Int. Ed. 2005, 44: 952
TesevicV. GladyszJA. J. Org. Chem. 2006, 71: 7433