Synlett 2007(20): 3226-3227  
DOI: 10.1055/s-2007-990918
SPOTLIGHT
© Georg Thieme Verlag Stuttgart · New York

Methy(trifluoromethyl)dioxirane (TFD): A Powerful and Versatile Oxidant in Organic Synthesis

Xu-Ye Tao*
The College of Chemistry & Material Science, Hebei Normal University, Shijiazhuang 050016, P. R. of China
e-Mail: taoxychem@sina.com.cn;
Further Information

Publication History

Publication Date:
03 December 2007 (online)

Introduction

During the last two decades, the use of dioxiranes as oxidants in organic synthesis has increased considerably. [1] Methyl(trifluoromethyl)dioxirane (TFD) has the highest reactivity among dioxiranes reported so far, and has been utilized for a broad variety of oxidative transformations in organic synthesis. Exemplary transformations are the monohydroxylation of alkanes, [2] chemoselective oxidation of allylic alcohols, [3] optically active sec,sec-1,2-diols [4] and simple sulfides, [5] oxyfunctionalization of unactivated tertiary and secondary C-H bonds of alkylamines [6] and aliphatic­ esters, [7] epoxidation of primary and secondary alkenylammonium salts [8] and chiral camphor N-enoylpyrazolidinones, [9] oxidative cleavage of acetals, ketals [10] and aryl oxazolines, [11] and conversion of cyclic ethers into lactones. [10] It is also found to be a useful reagent for the oxyfunctionalization of natural [12-14] and non-natural [15-19] targets, which include the direct hydroxylation at the side-chain C-25 of cholestane derivatives and vitamin D3 Windaus-Grundmann ketone, [12] high stereo- and regioselective conversion of vitamin D2 into its (all-R) tetraepoxide and C-25 hydroxy derivative, [13] stereoselective synthesis of (all-R)-vitamin D3 triepoxide and its 25-hydroxy derivative, [14] oxidation of centropolyindans, [15] buckminsterfullerene C60, [16] Binor S, [17] hydrocarbons bearing cyclopropyl moieties, [18] and selective bridgehead dihydroxylation of fenestrindane. [19]

    References

  • 1xa Adam W. Curci R. Edwards JO. Acc. Chem. Res.  1989,  22:  205 
  • 1xb Curci R. D’Accolti L. Fusco C. Acc. Chem. Res.  2006,  39:  1 
  • 1xc Murray RW. Chem. Rev.  1989,  89:  1187 
  • 1 Asebsio G. Mello R. González-Nú ez ME. Castellano G. Corral J. Angew. Chem., Int. Ed. Engl.  1996,  35:  217 
  • 2a Adam W. Paredes R. Smerz AK. Veloza LA. Eur. J. Org. Chem.  1998,  349 
  • 2b D’Accolti L. Fiorentino M. Fusco C. Rosa AM. Curci R. Tetrahedron Lett.  1999,  40:  8023 
  • 3 D’Accolti L. Detomaso A. Fusco C. Rosa A. Curci R. J. Org. Chem.  1993,  58:  3600 
  • 4 Asensio G. Mello R. González-Nú ez ME. Tetrahedron Lett.  1996,  37:  2299 
  • 5 Asensio G. González-Núez ME. Bernardini CB. Mello R. Adam W. J. Am. Chem. Soc.  1993,  115:  7250 
  • 6 Asensio G. Castallano G. Mello R. González-Núez ME. J. Org. Chem.  1996,  61:  5564 
  • 7 Asensio G. Mello R. Boix-Bernardini C. González-Núez ME. Castellano G. J. Org. Chem.  1995,  60:  3692 
  • 8 Fan CL. Lee W.-D. Teng N.-W. Sun Y.-C. Chen K. J. Org. Chem.  2003,  68:  9816 
  • 9 Voigt B. Porzel A. Golsch D. Adam W. Adam G. Tetrahedron  1996,  52:  10653 
  • 10 Yang D. Yip Y.-C. Wang X.-C. Tetrahedron Lett.  1997,  38:  7083 
  • 11 Bovicelli P. Lupattelli P. Mincione E. J. Org. Chem.  1992,  57:  5052 
  • 12 Curci R. Detomaso A. Lattanzio ME. Carpenter GB. J. Am. Chem. Soc.  1996,  118:  11089 
  • 13 Curci R. Detomaso A. Prencipe T. Carpenter GB. J. Am. Chem. Soc.  1994,  116:  8112 
  • 14 Kuck D. Schuster A. Fusco C. Fiorentino M. Curci R. J. Am. Chem. Soc.  1994,  116:  2375 
  • 15 Fusco C. Seraglia R. Curci R. J. Org. Chem.  1999,  64:  8363 
  • 16 D’Accolti L. Fusco C. Lucchini V. Carpenter GB. Curci R. J. Org. Chem.  2001,  66:  9063 
  • 17 D’Accolti L. Dinoi A. Fusco C. Curci R. J. Org. Chem.  2003,  68:  7806 
  • 18 Fusco C. Fiorentino M. Dinoi A. Curci R. J. Org. Chem.  1996,  61:  8681 
  • 19a Mello R. Fiorentino M. Sciacovelli O. Curci R. J. Org. Chem.  1988,  53:  3890 
  • 19b Mello R. González-Núez ME. Asensio G. Synlett  2007,  47 
  • 20a Mello R. Fiorentino M. Fusco C. Curci R. J. Am. Chem. Soc.  1989,  111:  6749 
  • 20b González-Nú ez ME. Royo J. Mello R. Báguena M. Ferrer JM. de Arellano CR. Asensio G. Prakash GKS. J. Org. Chem.  2005,  70:  7919 
  • 20c D’Accolti L. Fiorentino M. Fusco C. Capitelli F. Curci R. Tetrahedron Lett.  2007,  48:  3575 
  • 21a Mello R. Cassidei L. Fiorentino M. Fusco C. Hümmer W. Jäger V. Curci R. J. Am. Chem. Soc.  1991,  113:  2205 
  • 21b D’Accolti L. Fusco C. Annese C. Rella MR. Turteltaub JS. Williard PG. Curci R. J. Org. Chem.  2004,  69:  8510 
  • 22a Yang D. Wong M.-K. Yip Y.-C. J. Org. Chem.  1995,  60:  3887 
  • 23 D’Accolti L. Fiorentino M. Fusco C. Crupi P. Curci R. Tetrahedron Lett.  2004,  45:  8575 
  • 24 Paquette LA. Kreilein MM. Bedore MW. Friedrich D. Org. Lett.  2005,  7:  4665 
  • 25 Rella MR. Williard PG. J. Org. Chem.  2007,  72:  525