Download PDF
Synlett 2009(1): 9-22  
DOI: 10.1055/s-0028-1087478
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

The Stability/Reactivity Effects of Trifluoromethyl and Perfluoroalkyl Chains in a Masked 1,3-Dicarbonyl Derivative: The Case of 1-Acetoxy-1-iodo-2-(perfluoroalkyl)ethanes

Salem El Kharrat, Philippe Laurent*, Hubert Blancou
Institut des Biomolécules Max Mousseron, UMR-CNRS 5247 M.F.S.A., Université Montpellier 2, CC 1706, Place Eugène Bataillon, 34095 Montpellier Cedex 5, France
Fax: +33(4)67631046; e-Mail: philippe.laurent@univ-montp2.fr;
Further Information

Publication History

Received 22 May 2008
Publication Date:
12 December 2008 (online)

    Permissions and Reprints All articles of this category

Abstract

The development of an efficient and general trifluoro­methylation or perfluoroalkylation method is a major challenge in organic chemistry. This Account presents the breakthrough realized in this field using polyfluoroalkylated gem-iodoacetoxy derivatives which are useful synthons for the short preparation of various fluorinated organic compounds. The main body of this Account highlights several applications of these new derivatives as starting blocks for diverse regiospecific syntheses of trifluoromethyl- and perfluoroalkyl-containing heterocyclic compounds. A brief discussion of the use of a new method for the determination of the configuration and conformation of push-pull perfluoroalkyl-containing olefinic derivatives using coupling constant 4 J CF is included.

1 Introduction

2 Synthesis of α-Iodoalkyl Esters, R²R³C(I)OCOR¹

3 Reactivity of Polyfluoroalkylated gem-Iodoacetoxy Derivatives

3.1 Synthesis of 2-(Perfluoroalkyl)ethanals

3.2 Chemoselective Reactions

3.3 Reactivity Towards Nitrogen Compounds

3.4 Reactivity Towards Phenol Derivatives

3.5 Determination of the Stereochemistry of Push-Pull Derivatives Using a Through-Space Coupling Constant: 4 J CF

4 Summary and Outlook

Key words

aldehydes - fluorine - stereoselective synthesis - stereo­chemistry - heterocyclic compounds

    References

  • 1a Bégué J.-P. Bonnet-Delpon D. Chimie Bioorganique et Médicinale du Fluor   EDP Sciences/ CNRS Editions; Paris: 2005. 
  • 1b Kirsch P. Modern Fluoroorganic Chemistry   Wiley-VCH; Weinheim: 2004. 
  • 1c Welch JT. Tetrahedron  1987,  43:  3123 
    Search in Google Scholar
  • 1d Filler R. Organic Chemistry in Medicinal Chemistry and Biomedical Applications   Elsevier; Amsterdam: 1993. 
  • 2a Chambers RD. Fluorine in Organic Chemistry   Blackwell Publishing Ltd; Oxford UK: 2004. 
  • 2b Ismail FMD. J. Fluorine Chem.  2002,  118:  27 
    Search in Google Scholar
  • 2c Uneyama K. Organofluorine Chemistry   Blackwell Publishing Ltd; Oxford UK: 2006. 
  • 2d Elliott AJ. In Chemistry of Organic Fluorine Compounds II: A Critical Review   Hudlicky M. Pavlath AE. ACS Monograph 187; Washington DC: 1995.  p.1119-1125  
  • 2e Chambers RD. Holling D. Sandford G. Batsanov AS. Howard JAK. J. Fluorine Chem.  2004,  125:  661 
    Search in Google Scholar
  • 3a Park BK. Kitteringham NR. O’Neill PM. Annu. Rev. Pharmacol. Toxicol.  2001,  41:  443 
    Search in Google Scholar
  • 3b Böhm H.-J. Banner D. Bendels S. Kansy M. Kuhn B. Müller K. Obst-Sander U. Stahl M. ChemBioChem  2004,  5:  637 
    Search in Google Scholar
  • 3c Gerebtzoff G. Li-Blatter X. Fischer H. Frentzel A. Seelig A. ChemBioChem  2004,  5:  676 
    Search in Google Scholar
  • 3d Alkorta I. Rozas I. Elguero J. J. Fluorine Chem.  2000,  101:  233 
    Search in Google Scholar
  • 3e Rozen S. Acc. Chem. Res.  1996,  29:  243 
    Search in Google Scholar
  • 3f Bégué J.-P. Bonnet-Delpon D. ChemMedChem  2007,  2:  608 
    Search in Google Scholar
  • 3g Pasqui F. Canfarini F. Giolitti A. Guidi A. Pestellini V. Arcamone F. Tetrahedron  1996,  52:  185 
    Search in Google Scholar
  • 3h Wolf W. Presant CA. Waluch V. Adv. Drug Delivery Rev.  2000,  41:  55 
    Search in Google Scholar
  • 4a Sandford G. Philos. Trans. R. Soc. London, Ser. A.  2000,  358:  455 
    Search in Google Scholar
  • 4b Uneyama K. Organofluorine Chemistry   Blackwell Publishing Ltd; Oxford UK: 2006. 
  • 4c Banks RE. Smart BE. Tatlow JC. Organofluorine Chemistry: Principles and Commercial Applications   Plenum Press; New York: 1994. 
  • 4d Olah GA. Chambers RD. Prakash GKS. Synthetic Fluorine Chemistry   Wiley-Interscience; New York: 1992. 
  • 4e Soloshonok VA. Enantiocontrolled Synthesis of Fluoro-Organic Compounds   Wiley & Sons; Chichester, England: 1999. 
  • 5a Krebs A. In Houben-Weyl   Vol. E 14a/3:  Hagemann H. Klamann D. Thieme; Stuttgart: 1992.  p.85 
    Search in Google Scholar
  • 5b Zakrzewski J. Chromatographia  2004,  59:  775 
    Search in Google Scholar
  • 5c Geraghty NWA. In Comprehensive Organic Functional Group Transformations   Vol. 4:  Katritzky AR. Meth-Cohn O. Rees CW. Kirby GW. Pergamon, Elsevier Science Ltd.; Cambridge, UK: 1995.  p.51-58  
    Search in Google Scholar
  • 5d Bigler P. Muhle H. Neuenschwander M. Synthesis  1978,  593 
  • 5e Michie JK. Miller JA. J. Chem. Soc., Perkin Trans. 1  1981,  785 
  • 5f Campbell AC. Maidment MS. Pick JH. Stevenson DFM. J. Chem. Soc., Perkin Trans. 1  1985,  1567 
  • 6a Euranto EK. Kujanpaa T. Acta Chem. Scand.  1961,  15:  1209 
    Search in Google Scholar
  • 6b Schenk WK. Kyburz R. Neuenschwander M. Helv. Chim. Acta  1975,  58:  1099 
    Search in Google Scholar
  • 6c Neuenschwander M. Schenk WK. Kyburz R. Chimia  1971,  25:  361 
    Search in Google Scholar
  • 6d Neuenschwander M. Schenk WK. Chimia  1972,  26:  194 
    Search in Google Scholar
  • 6e Campbell AC. Maidment MS. Pick JH. Stevenson DFM. J. Chem. Soc., Perkin Trans. 1  1985,  1567 
  • 6f Bhatt MV. Kamath KM. Ravindranathan M. J. Chem. Soc. C  1971,  1772 
  • 6g Hughes MJ. Thomas EJ. J. Chem. Soc., Perkin Trans. 1  1993,  1493 
  • 6h Euranto EK. Leppanen O. Acta Chem. Scand.  1963,  17:  2765 
    Search in Google Scholar
  • 6i Euranto EK. Noponen A. Kujanpaa T. Acta Chem. Scand.  1966,  20:  1273 
    Search in Google Scholar
  • 7a Kamachi H. Okita T. Okuyama S. Hoshi H. Naito T. J. Antibiot.  1990,  43:  1564 
    Search in Google Scholar
  • 7b Buckley E. Whittle E. Can. J. Chem.  1962,  40:  1611 
    Search in Google Scholar
  • 7c Oszczapowicz I. Tejchman B. Zimniak A. Oszczapowicz J. Acta Pol. Pharm.  1998,  55:  197 
    Search in Google Scholar
  • 8a Bodor N. Sloan KB. Kaminski JJ. Shih C. Pogany S. J. Org. Chem.  1983,  48:  5280 
    Search in Google Scholar
  • 8b Knochel P. Chou T.-S. Jubert C. Rajagopal D. J. Org. Chem.  1993,  58:  588 
    Search in Google Scholar
  • 8c Thomson W. Nicholls D. Mitchell AG. Corner JA. Irwin WJ. Freeman S. J. Chem. Soc., Perkin Trans. 1  1993,  2303 
  • 8d Bhatt MV. Kamath KM. Ravindranathan M. J. Chem. Soc. C  1971,  3344 
  • 9 Andreades S. England DC. J. Am. Chem. Soc.  1961,  83:  4670 
    CrossrefSearch in Google Scholar
  • 10a Brace NO. J. Org. Chem.  1962,  27:  3033 
    Search in Google Scholar
  • 10b Brace NO. J. Fluorine Chem.  1999,  93:  1 
    Search in Google Scholar
  • 10c Brace NO. inventors; US Patent  3,016,407. 
  • 10d Brace NO. inventors; US Patent  3.145,222. 
  • 10e Brace NO. J. Org. Chem.  1962,  27:  4491 
    Search in Google Scholar
  • 11a Napoli M. Fraccaro C. Conte L. Gambaretto GP. Legnaro E. J. Fluorine Chem.  1992,  57:  219 
    Search in Google Scholar
  • 11b Napoli M. Scipioni A. Conte L. Legnaro E. Krotz LN. J. Fluorine Chem.  1994,  66:  249 
    Search in Google Scholar
  • 11c Napoli M. Fraccaro C. J. Fluorine Chem.  2001,  111:  49 
    Search in Google Scholar
  • 12 Li A.-R. Chen Q.-Y. J. Fluorine Chem.  1997,  81:  99 
    CrossrefSearch in Google Scholar
  • 13a Laurent P. Blancou H. Commeyras A. Tetrahedron Lett.  1992,  33:  2489 
    Search in Google Scholar
  • 13b Laurent P. Blancou H. Commeyras A. J. Fluorine Chem.  1993,  62:  161 
    Search in Google Scholar
  • 14a Laurent P. Blancou H. Commeyras A. J. Fluorine Chem.  1993,  62:  173 
    Search in Google Scholar
  • 14b Miller RD. Michl J. Chem. Rev.  1989,  89:  1359 
    Search in Google Scholar
  • 14c Alexander ER. Ionic Organic Reactions   Wiley & Sons; New York: 1950.  p.245 
  • 14d Heath JR. Science (Washington, D.C.)  1992,  258:  1131 
    Search in Google Scholar
  • 14e Jiang Y. Wu Y. Zhong S. Xu C. Yu W. Xie Y. Qian Y. J. Am. Chem. Soc.  2000,  122:  12383 
    Search in Google Scholar
  • 14f Li YD. Qian YT. Liao HW. Ding Y. Xu CY. Li FQ. Zhou GE. Science (Washington, D.C.)  1998,  281:  246 
    Search in Google Scholar
  • 14g Baldwin RK. Pettigrew KA. Garno JC. Power PP. Liu GY. Kauziarich SM. J. Am. Chem. Soc.  2002,  124:  1150 
    Search in Google Scholar
  • 15a Takeyama Y. Ichinose Y. Oshima K. Utimoto K. Tetrahedron Lett.  1989,  30:  3159 
    Search in Google Scholar
  • 15b Huang B.-N. Haas A. Lieb M. J. Fluorine Chem.  1986,  36:  49 
    Search in Google Scholar
  • 15c Wang Z. Lu X. Tetrahedron  1995,  51:  2639 
    Search in Google Scholar
  • 16a Anderson CB. Sepp DT. J. Org. Chem.  1967,  32:  607 
    Search in Google Scholar
  • 16b Jung ME. Mazurek MA. Lim RM. Synthesis  1978,  588 
  • 17 Calleja S. Laurent P. Blancou H. J. Fluorine Chem.  2005,  126:  1493 
    CrossrefSearch in Google Scholar
  • 18a Krapcho AP. Lovey AJ. Tetrahedron Lett.  1973,  957 
  • 18b Olah GA. Welch J. J. Am. Chem. Soc.  1975,  97:  208 
    Search in Google Scholar
  • 19a Lehmler HJ. Chemosphere  2005,  58:  1471 
    Search in Google Scholar
  • 19b Dinglasan MJA. Ye Y. Edwards EA. Mabury SA. Environ. Sci. Technol.  2004,  38:  2857 
    Search in Google Scholar
  • 19c Rocaboy C. Bauer W. Gladysz JA. Eur. J. Org. Chem.  2000,  2621 
  • 19d Pozzi G. Quici S. Shepperson I. Tetrahedron Lett.  2002,  43:  6141 
    Search in Google Scholar
  • 19e Leveque L. Le Blanc M. Pastor R. Tetrahedron Lett.  1998,  39:  8857 
    Search in Google Scholar
  • 20a El Kharrat S. Laurent P. Blancou H. Reactivity of RFCH2CHIOAc, Reaction with Aniline and Phenol.   European Symposium on Fluorine Chemistry; Bordeaux France:
  • 20b El Kharrat S. Skander M. Dahmani A. Laurent P. Blancou H. Reactivity of gem-Iodoacetoxy-perfluoroethylethane. International Symposium on Biomolecules and Related Compounds   Max Mousseron Institute; Montpellier France: March 2005. 
  • 21 Laurent P. Tra Ahn D. Blancou H. Commeyras A. J. Fluorine Chem.  1999,  94:  139 
    Search in Google Scholar
  • 23 El Kharrat S. Skander M. Dahmani A. Laurent P. Blancou H. J. Org. Chem.  2005,  70:  8327 
    CrossrefSearch in Google Scholar
  • 24a Keller H. Schlosser M. Tetrahedron  1996,  52:  4637 
    Search in Google Scholar
  • 24b Gagan JMF. Lloyd D. Chem. Commun.  1967,  1043 
  • 24c Lloyd D. Gagan JMF. J. Chem. Soc. C  1970,  2488 
  • 25a Knop A. Pilato LA. Phenolic Resins - Chemistry, Applications and Performance   Springer-Verlag; New York: 1985. 
  • 25b Fraser DA. Hall RW. Raum ALJ. J. Appl. Chem.  1957,  7:  676 
    Search in Google Scholar
  • 25c Dragi E. Casiraghi G. Sartori G. Casnati G. Macromolecules  1978,  11:  1295 
    Search in Google Scholar
  • 25d Motawie AM. Sadek EM. Polym. Adv. Technol.  1999,  10:  223 
    Search in Google Scholar
  • 25e Shi N. Thermosetting Resin  2000,  15:  30 
    Search in Google Scholar
  • 25f Kinjo N. Ogata M. Nishi K. Kaneda A. Adv. Polym. Sci.  1989,  88:  1 
    Search in Google Scholar
  • 25g Tsigdinos GA. Top. Curr. Chem.  1978,  76:  1 
    Search in Google Scholar
  • 25h Corma A. Chem. Rev.  1997,  97:  2373 
    Search in Google Scholar
  • 25i Jana SK. Kugita T. Namba S. Appl. Catal., A  2004,  266:  245 
    Search in Google Scholar
  • 26a Neuworth MB. Laufer RJ. Barnhart JW. Sefranka JA. McIntoch DD. J. Med. Chem.  1970,  13:  722 
    Search in Google Scholar
  • 26b Taguet A. Ameduri B. Boutevin B. Adv. Polym. Sci.  2005,  184:  127 
    Search in Google Scholar
  • 26c Cassidy PE. Hougham GG. Johns K. Davidson T. Fluoropolymers 1: Synthesis   Kluwer Academic Publishers; New York: 1999. 
  • 26d Extrand CW. J. Fluorine Chem.  2003,  122:  121 
    Search in Google Scholar
  • 26e DeBergalis M. J. Fluorine Chem.  2004,  125:  1255 
    Search in Google Scholar
  • 27 El Kharrat S. Laurent P. Blancou H. J. Org. Chem.  2006,  71:  6742 
    CrossrefSearch in Google Scholar
  • 28 El Kharrat S, Laurent P, and Blancou H. inventors; PCT Patent  FR2005000863.  ; Chem. Abstr. 2005, 143, 386772
  • 29a Kona J. Zahradnik P. Fabian WMF. J. Org. Chem.  2001,  66:  4998 
    Search in Google Scholar
  • 29b Bernasconi CF. Tetrahedron  1989,  45:  4017 
    Search in Google Scholar
  • 29c Kona J. Fabian WMF. Zahradnik P. J. Chem. Soc., Perkin Trans. 2  2001,  422 
  • 29d Brenasconi CF. Ketner RJ. Chen X. Rappoport Z. J. Am. Chem. Soc.  1998,  120:  7461 
    Search in Google Scholar
  • 29e Davidson DN. English RB. Kaye PT. J. Chem. Soc., Perkin Trans. 2  1991,  1509 
  • 29f Xu L.-W. Li J.-W. Zhou S.-L. Xia C.-G. New J. Chem.  2004,  28:  183 
    Search in Google Scholar
  • 29g Zheng J.-C. Liao W.-W. Tang Y. Sun X.-L. Dai L.-X. J. Am. Chem. Soc.  2005,  127:  12222 
    Search in Google Scholar
  • 29h Van Lingen HL. Zhuang W. Hansen T. Rutjes FPJT. Jørgensen KA. Org. Biomol. Chem.  2003,  1:  1953 
    Search in Google Scholar
  • 29i Farnworth MV. Cross MJ. Louie J. Tetrahedron Lett.  2004,  45:  7441 
    Search in Google Scholar
  • 29j Kona J. Zahradnik P. Fabian WMF. J. Org. Chem.  2001,  66:  4998 
    Search in Google Scholar
  • 29k Berner AM. Tedeschi L. Enders D. Eur. J. Org. Chem.  2002,  1877 
  • 30 El Kharrat S. Laurent P. Blancou H. J. Org. Chem.  2006,  71:  8637 
    CrossrefSearch in Google Scholar
  • 31 El Kharrat S. El Kharrat R. Laurent P. Blancou H. Synthesis  2007,  3542 
    Thieme Connect
  • 32a Peralta JE. Barone V. Contreras RH. Zaccari DG. Snyder JP. J. Am. Chem. Soc.  2001,  123:  9162 
    Search in Google Scholar
  • 32b Bégué J.-P. Bonnet-Delpon D. Mesureur D. Ourévitch M. Magn. Reson. Chem.  1991,  29:  675 
    Search in Google Scholar
  • 32c Gakh YG. Gakh AA. Gronenborn AM. Magn. Reson. Chem.  2000,  38:  551 
    Search in Google Scholar
  • 32d Hilton J. Sutcliffe LH. In Progress in Nuclear Magnetic Resonance Spectroscopy   Vol. 10:  Emsly JW. Feeney J. Sutcliffe LH. Pergamon Press; Oxford: 1975.  p.27 
    Search in Google Scholar
  • 32e Hsee LC. Sardella DJ. Magn. Reson. Chem.  1990,  28:  688 
    Search in Google Scholar
  • 32f Contreras RH. Giribet CG. Natiello MA. Pérez J. Rae ID. Weigold JA. Aust. J. Chem.  1985,  38:  1779 
    Search in Google Scholar
  • 32g Rae ID. Staffa A. Diz AC. Giribet CG. Ruiz de Azua MC. Contreras RH. Aust. J. Chem.  1987,  40:  1923 
    Search in Google Scholar
  • 32h Rae ID. Weigold JA. Contreras RH. Yamamoto G. Magn. Reson. Chem.  1992,  30:  1047 
    Search in Google Scholar
  • 32i Davis DR. Lutz RP. Roberts JD. J. Am. Chem. Soc.  1961,  83:  246 
    Search in Google Scholar
  • 32j Petrakis L. Sederholm CH. J. Am. Chem. Soc.  1961,  83:  1243 
    Search in Google Scholar
  • 33a Malecka M. J. Mol. Struct.  2007,  831:  135 
    Search in Google Scholar
  • 33b Kleinpeter E. J. Serb. Chem. Soc.  2006,  71:  1 
    Search in Google Scholar
  • 33c Salon J. Milata V. Gatial A. Pronayova N. Lesko J. Cernuchova P. Rappoport Z. Vo-Thanh G. Loupy A. Eur. J. Org. Chem.  2005,  4870 
  • 33d Kozerski L. Kwiecien B. Kaweçki R. Urbanczyk-Lipkowaska Z. Bocian W. Bednarek E. Sitkowski J. Maurin J. Pazderski L. Hansen PE. New J. Chem.  2004,  28:  1562 
    Search in Google Scholar
  • 33e Pappalardo RR. Sanchez Marcos E. Ruiz-Lopez M. Rinaldi D. Rivail J.-L. J. Am. Chem. Soc.  1993,  115:  3722 
    Search in Google Scholar
  • 33f Lammertsma K. Bharatam PV. J. Org. Chem.  2000,  65:  4662 
    Search in Google Scholar
  • 33g Vay PM. Chem. Commun.  1969,  861 
  • 33h Bodendorf K. Mayer R. Chem. Ber.  1965,  98:  3561 
    Search in Google Scholar
  • 34a Frieden C. Hoeltzli SD. Ropson I. Protein Sci.  1993,  2:  2007 
    Search in Google Scholar
  • 34b Chiu H.-P. Suzuki Y. Gullickson D. Ahmad R. Kokona B. Fairman R. Cheng RP. J. Am. Chem. Soc.  2006,  128:  15556 
    Search in Google Scholar
  • 34c Jäckel C. Koksch B. Eur. J. Org. Chem.  2005,  4483 
  • 34d Jäckel C. Seufert W. Thust S. Koksch B. ChemBioChem  2004,  5:  717 
    Search in Google Scholar
  • 34e Bann JG. Pinkner J. Hultgren SJ. Frieden C. Proc. Natl. Acad. Sci. U.S.A.  2002,  99:  709 
    Search in Google Scholar
  • 34f Danielson MA. Falke JJ. Annu. Rev. Biophys. Biomol. Struct.  1996,  25:  163 
    Search in Google Scholar
  • 34g Dyson HJ. Wright PE. Annu. Rev. Phys. Chem.  1996,  47:  369 
    Search in Google Scholar
22

Laurent, P.; Biancou, H., unpublished results.