Synlett 2006(20): 3550-3551  
DOI: 10.1055/s-2006-956469
SPOTLIGHT
© Georg Thieme Verlag Stuttgart · New York

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

Majid Rezaeivalla*
Faculty of Chemistry, Bu-Ali Sina University, Hamadan 6517838683, Iran
e-Mail: mrezaeivala@gmail.com;

Further Information

Publication History

Publication Date:
08 December 2006 (online)

Biographical Sketches

Majid Rezaeivalla was born in Hamadan, Iran in 1975. He received his B.Sc. in chemistry from Bu-Ali Sina University, Hamadan, Iran in 1998, and his M.Sc. in inorganic chemistry under the supervision of Dr. Mojtaba Bagherzadeh from the same university in 2002. He is currently working towards his Ph.D. under the supervision of Prof. Hassan Keypour. His research interests focus on the synthesis and characterization of new macroacyclic Schiff base ligands and ­related complexes and their applications 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]

Abstracts

(A) NaIO4/DMF oxidizes various primary and secondary halides to the corresponding aldehydes and ketones under mild conditions (150 °C, 40-60 min) in high yields (70-90%). [6]

(B) A mild and efficient method for the deprotection of silyl ethers is reported. The most often used silyl protecting groups, such as TBDMS, TIPS, TMS, TES, TIBS, and TPS can be cleaved by NaIO4 furnishing the corresponding alcohol in high yield. This method can be used for a wide range of substrates. [7]

(C) A highly stereoselective epoxidation (>95%) of unfunctionalized alkenes was performed by tetrabutylammonium periodate in the presence of six different phenyl-substituted manganese(III) meso-tetraphenylporphyrins [Mn(Por)] and imidazole in CH2Cl2. [8]

(D) Sodium periodate mediates the C-H activation of alkyl­benzenes and alkanes with LiBr efficiently under acidic conditions, producing the corresponding bromo and acetoxy derivatives in excellent yields. [9]

(E) NaIO4 oxidizes alkali metal halides efficiently in aqueous ­medium to halogenate alkenes and aromatics and produce the ­corresponding halo derivatives in excellent regio- and stereoselectivity. The system also demonstrates the asymmetric version of bromo hydroxylation using α-cyclodextrin complexes, resulting in moderate ee values. [10]

(F) Cleavage of the O-(dimethoxytrityl) group using neutral ­sodium periodate is reported. [11] Sodium periodate in aqueous ­organic solvents selectively removes the O-(dimethoxytrityl) ­protecting group under mild reaction conditions. The selectivity of the cleavage was studied using the nucleoside derivatives pro­tected by various types of groups commonly used in nucleoside and nucleotide chemistry. [11]

(G) Oxidative cleavage of a series of glycols using NaIO4 on silica gel in the presence of a series of stabilized ylides provides access to a number of synthetically useful alkenes. The ease and general utility of this reaction is demonstrated here using several carbo­hydrates and amino acids. [12]

    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 

    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 

Figure 1