Synlett 2007(17): 2764-2765  
DOI: 10.1055/s-2007-991080
SPOTLIGHT
© Georg Thieme Verlag Stuttgart · New York

[Hydroxy(tosyloxy)iodo]benzene (HTIB)

Rajesh Kumar*
Department of Chemistry, Kurukshetra University, Kurukshetra, Haryana 136119, India
e-Mail: rajesh_chem12a@rediffmail.com;

Further Information

Publication History

Publication Date:
27 September 2007 (online)

Biographical Sketches

Rajesh Kumar was born in 1980 at Karsa Dod, Haryana, India. He received his B.Sc. and M.Sc. degrees in chemistry with ­specialization in organic chemistry from Kurukshetra University, Kurukshetra, Haryana, India. Presently he is working as a Senior Research Fellow (CSIR-SRF) towards his PhD under the super­vision of Prof. Om Prakash at Kurukshetra University. His research work is focused on the synthetic utility of hypervalent iodine(III) ­reagents in organic synthesis.

Introduction

[Hydroxy(tosyloxy)iodo]benzene (HTIB), one of the most significant reagents among the family of hypervalent iodine reagents, has been widely used as an effective ­oxidant in the synthesis of various organic compounds. HTIB was first discovered in 1970 by Neiland and Karele. [1] A few years later, Koser and co-workers discovered that HTIB is an efficient reagent in organic synthesis, so in contemporary literature HTIB is often referred to as ‘Koser’s Reagent’.

Preparation:

Properties:

Abstracts

(A) A facile, general and high-yielding protocol for the synthesis of novel α-tosyloxy β-keto sulfones is described utilizing the ­relatively non-toxic HTIB under solvent-free conditions at room temperature. [2]

(B) Reaction of various ketones with HTIB followed by treatment of the α-tosyloxy ketones thus generated in situ with sodium azide, possibly in the presence of a phase-transfer catalyst, at room ­temperature offers a one-pot procedure for the synthesis of α-azido ketones. [3] [4]

(C) Ketones react with HTIB in DMSO-H2O to afford α-hydroxy ketones under neutral conditions and in good yields. [5]

(D) Spirodienones bearing a 1-azaspiro[4.5]decane ring have been synthesized from N-methoxy-(4-halogenophenyl)amides by the intramolecular ipso attack of a nitrenium ion generated with HTIB in trifluoroethanol. [6]

(E) The treatment of aryl alkenes with HTIB in 95% methanol affords the corresponding α-aryl ketones. This oxidative rearrangement is general for acyclic and cyclic aryl alkenes and permits regioselective synthesis of isomeric α-phenyl ketone pairs. [7]

(F) Polycyclic aromatic hydrocarbons (PAH) undergo regioselective oxidative substitution with HTIB in dichloromethane to give the corresponding aryl sulfonate esters. [8]

(G) Oxidation of 3-cinnamoyl-4-hydroxy-6-methyl-2H-pyran-2-ones with HTIB in CH2Cl2 leads to cyclization, thereby providing a new and convenient route for the synthesis of 3-aryl-7-methylpyrano[4,3-b]pyran-4H,5H-diones. [9]

(H) Oxidation of flavanones to flavones was developed using HTIB in ionic liquid 1,3-di-n-butylimidazolium bromide at room temperature. [10]

(I) The oxidation of benzylic alcohols with HTIB provides a rapid and convenient method to prepare corresponding carbonyl compounds under solvent-free conditions. [11]

(J) A novel and direct method for the synthesis of α-halocarbonyl compounds using sequential treatment of carbonyl compounds with HTIB followed by magnesium halides under solvent-free conditions. [12]

    References

  • 1 Neiland O. Karele B. J. Org. Chem. USSR (Engl. Transl.)  1970,  6:  889 
  • 2 Kumar D. Sundaree S. Patel G. Rao VS. Varma RS. Tetrahedron Lett.  2006,  47:  8239 
  • 3 Prakash O. Pannu K. Prakash R. Batra A. Molecules  2006,  11:  523 
  • 4 Kumar D. Sundaree S. Rao VS. Synth. Commun.  2006,  36:  1893 
  • 5 Xie YY. Chen ZC. Synth. Commun.  2002,  32:  1875 
  • 6 Miyazawa E. Sakamoto T. Kikugawa Y. J. Org. Chem.  2003,  68:  5429 
  • 7 Justik MW. Koser GF. Tetrahedron Lett.  2004,  45:  6159 
  • 8 Koser GF. Telu S. Laali KK. Tetrahedron Lett.  2006,  47:  7011 
  • 9 Prakash O. Kumar A. Sadana AK. Singh SP. Synthesis  2006,  21 
  • 10 Muthukrishnan M. Patil PS. More SV. Joshi RA. Mendeleev Commun.  2005,  100 
  • 11 Lee JC. Lee JY. Lee SJ. Tetrahedron Lett.  2004,  45:  4939 
  • 12 Lee JC. Park JY. Yoon SY. Bae YH. Lee SJ. Tetrahedron Lett.  2004,  45:  191 

    References

  • 1 Neiland O. Karele B. J. Org. Chem. USSR (Engl. Transl.)  1970,  6:  889 
  • 2 Kumar D. Sundaree S. Patel G. Rao VS. Varma RS. Tetrahedron Lett.  2006,  47:  8239 
  • 3 Prakash O. Pannu K. Prakash R. Batra A. Molecules  2006,  11:  523 
  • 4 Kumar D. Sundaree S. Rao VS. Synth. Commun.  2006,  36:  1893 
  • 5 Xie YY. Chen ZC. Synth. Commun.  2002,  32:  1875 
  • 6 Miyazawa E. Sakamoto T. Kikugawa Y. J. Org. Chem.  2003,  68:  5429 
  • 7 Justik MW. Koser GF. Tetrahedron Lett.  2004,  45:  6159 
  • 8 Koser GF. Telu S. Laali KK. Tetrahedron Lett.  2006,  47:  7011 
  • 9 Prakash O. Kumar A. Sadana AK. Singh SP. Synthesis  2006,  21 
  • 10 Muthukrishnan M. Patil PS. More SV. Joshi RA. Mendeleev Commun.  2005,  100 
  • 11 Lee JC. Lee JY. Lee SJ. Tetrahedron Lett.  2004,  45:  4939 
  • 12 Lee JC. Park JY. Yoon SY. Bae YH. Lee SJ. Tetrahedron Lett.  2004,  45:  191