Sodium Periodate (NaIO₄) -A Versatile Reagent in Organic Synthesis

Introduction

Sodium periodate (sodium metaperiodate), NaIO₄ (mp 300 °C; Figure 1), is commercially available and is applied mainly in aqueous or aqueous-alcoholic solutions. Like the free periodic acid, sodium periodate cleaves ­vicinal diols to carbonyl compounds. [1] The popularity stems from its specificity, its reactivity under neutral and mild ­conditions which is compatible with a wide range of functionalities, its stability, and its low cost. [2] Sulfides are transformed by sodium periodate into sulfoxides. It is also a reoxidant of lower-valency ruthenium in oxidations with ruthenium tetroxide. [3]

Figure 1

Tetrabutylammonium periodate, (n-Bu)₄NIO₄ (mp 175 °C), which is usually prepared in situ from tetrabutyl­ammonium hydrogen sulfate and sodium periodate, [4] is useful in two-phase systems, because it dissolves in ­chloroform and other organic solvents. [3] It is used in ­homogeneous oxidations of sulfides, 2-hydroxy acids, and α-bromoketones. [5]

References

• 1 Wolfrom ML. Yosizawa Z. J. Am. Chem. Soc.  1959,  81:  3477 
• 2a Marco-Contelles J. Destabel C. Gallego P. Chiara JL. Bernabe M. J. Org. Chem.  1996,  61:  1354 
• 2b Shing TKM. Wong CH. Yip T. Tetrahedron: Asymmetry  1996,  7:  1323 
• 2c Wipf P. Kim Y. Goldstein DM. J. Am. Chem. Soc.  1995,  117:  10587 
• 2d Zhong Y.-L. Shing TKM. J. Org. Chem.  1997,  62:  2622 
• 2e Shing TKM. In Comprehensive Organic Synthesis   Vol. 7:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991.  p.703 
• 3 Liu K.-T. Tong Y.-C. J. Org. Chem.  1978,  43:  2717 
• 4 Hudlicky M. Oxidation in Organic Chemistry   ACS; Washington: 1990. 
• 5 Santaniello E. Manzocchi A. Farachi C. Synthesis  1980,  563 
• 6 Das S. Panigrahi AK. Maikap GC. Tetrahedron Lett.  2003,  44:  1375 
• 7 Wang M. Li C. Liang X. Tetrahedron Lett.  2003,  43:  8727 
• 8a Mohajer D. Karimipour G. Bagherzadeh M. New J. Chem.  2004,  28:  740 
• 8b Mohajer D. Bagherzadeh M. J. Chem. Res., Synop.  1998,  556 
• 9 Shaikh TM. Sudalai A. Tetrahedron Lett.  2005,  46:  5589 
• 10 Dewkar GK. Narina SV. Sudalai A. Org. Lett.  2003,  5:  4501 
• 11 Rejman D. Kralikova S. Tocik Z. Liboska R. Rosenberg I. Collect. Czech. Chem. Commun.  2002,  67:  502 
• 12 Dunlap NK. Mergo W. Jones JM. Carrick JD. Tetrahedron Lett.  2002,  43:  3923