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Synthesis 2007(16): 2581-2584  
DOI: 10.1055/s-2007-983779
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© Georg Thieme Verlag Stuttgart · New York

3-(Perfluoroalkyl)propanols: Valuable Building Blocks for Fluorous Chemistry

József Rábai*, Csongor Szíjjártó, Peter Ivanko, Dénes Szabó
Department of Organic Chemistry, Institute of Chemistry, Eötvös Loránd University, P. O. Box 32, 1518 Budapest 112, Hungary
Fax: +36(1)3722592; e-Mail: rabai@elte.hu;
Further Information

Publication History

Received 26 February 2007
Publication Date:
12 July 2007 (online)

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Abstract

2-Iodo-3-(perfluoroalkyl)propanols are obtained in excellent yields and several-hundred-gram quantities by the controlled radical addition of commercially available n-perfluoroalkyl and perfluoroisoalkyl iodides to allyl alcohol. Their consecutive reduction with hydrazine hydrate and Raney nickel catalyst in methanol afforded the corresponding 3-(perfluoroalkyl)propanols in high yields and purity.

Key words

alkyl halides - alcohols - fluorine - reductive dehalogenation - transfer hydrogenation

    References

  • 1a Horváth IT. Rábai J. Science  1994,  266:  72 
    CrossrefGoogle Scholar
  • 1b Horváth IT, and Rábai J. inventors; US  5,463,082.  ; Chem. Abstr. 1995, 123, 87349
    Crossref
  • 2 Studer A. Hadida S. Ferritto R. Kim S.-Y. Jeger P. Wipf P. Curran DP. Science  1997,  275:  823 
    CrossrefGoogle Scholar
  • 3 Oderaotoshi Y. Zhang Q. Luo Z. Curran DP. Science  2001,  291:  1766 
    CrossrefPubMedGoogle Scholar
  • 4 Rábai J. In Handbook of Fluorous Chemistry   Gladysz JA. Curran DP. Horváth IT. Wiley-VCH; Weinheim: 2004.  Chap. 9.
    Google Scholar
  • 5a Horváth IT. Acc. Chem. Res.  1998,  31:  641 
    CrossrefGoogle Scholar
  • 5b Rábai J. Szlávik Z. Horváth IT. In Handbook of Green Chemistry and Technology   Clark J. MacQuarrie D. Blackwell Science; Oxford: 2002.  Chap. 21. p.502-523  
    CrossrefGoogle Scholar
  • 5c

    Special issue on Fluorous Chemistry: Tetrahedron 2002, 58, 3823-4131.
    Crossref
  • 5d Handbook of Fluorous Chemistry   Gladysz JA. Curran DP. Horváth IT. Wiley-VCH; Weinheim: 2004. 
    CrossrefGoogle Scholar
  • 5e Andrushko V. Schwinn D. Tzschucke CC. Michalek F. Horn J. Mössner C. Bannwarth W. Helv. Chim. Acta  2005,  88:  936 
    CrossrefGoogle Scholar
  • 5f Pearson WH. Berry DA. Stoy P. Jung K.-Y. Sercel AD. J. Org. Chem.  2005,  70:  7114 
    CrossrefGoogle Scholar
  • 5g

    Special issue on Fluorous Chemistry: QSAR Comb. Sci. 2006, 25, 679-806.
    Crossref
  • 6a Horváth IT. Kiss G. Cook RA. Bond JE. Stevens PA. Rábai J. Mozeleski EJ. J. Am. Chem. Soc.  1998,  120:  3133 
    CrossrefGoogle Scholar
  • 6b Szlávik Z. Tárkányi G. Gömöry Á. Tarczay G. Rábai J. J. Fluorine Chem.  2001,  108:  7 
    CrossrefGoogle Scholar
  • 6c Gladysz JA. Ponytails: Structural and Electronic Considerations, In Handbook of Fluorous Chemistry   Gladysz JA. Curran DP. Horváth IT. Wiley-VCH; Weinheim: 2004.  Chap. 5.
    CrossrefGoogle Scholar
  • 8a Miura T. Hirose Y. Ohmae M. Inazu T. Org. Lett.  2001,  3:  3947 
    CrossrefGoogle Scholar
  • 8b Mizuno M. Goto K. Miura T. Matsuura T. Inazu T. Tetrahedron Lett.  2004,  45:  3425 
    CrossrefGoogle Scholar
  • 8c Goto K. Miura T. Mizuno M. Tetrahedron Lett.  2005,  46:  8293 
    CrossrefGoogle Scholar
  • 8d Miura T. Satoh A. Goto K. Murakami Y. Imai N. Inazu T. Tetrahedron: Asymmetry  2005,  16:  3 
    CrossrefGoogle Scholar
  • 8e Vlád G. Richter FU. Horváth IT. Tetrahedron Lett.  2005,  46:  8605 
    CrossrefGoogle Scholar
  • 8f Emnet C. Gladysz JA. Synthesis  2005,  1012 
    CrossrefGoogle Scholar
  • 8g Fustero S. Sancho AG. Chiva G. Sanz-Cervera JF. del Pozo C. Acena JL. J. Org. Chem.  2006,  71:  3299 
    CrossrefGoogle Scholar
  • 8h Zhang W. Curran DP. Tetrahedron  2006,  62:  11837 ; and references therein
    CrossrefGoogle Scholar
  • 8i Mizuno M. Matsumoto H. Goto K. Hamasaki K. Tetrahedron Lett.  2006,  47:  8831 
    CrossrefGoogle Scholar
  • 8j Kojima M. Nakamura Y. Ishikawa T. Takeuchi S. Tetrahedron Lett.  2006,  47:  6309 
    CrossrefGoogle Scholar
  • 8k Bayardon J. Holczknecht O. Pozzi G. Sinou D. Tetrahedron: Asymmetry  2006,  17:  1568 
    CrossrefGoogle Scholar
  • 8l Zhang W. Williams JP. Lu Y. Nagashima T. Chu Q. Tetrahedron Lett.  2007,  48:  563 
    CrossrefGoogle Scholar
  • From CF3CH2CH2MgCl and (EtO)3CH, see:
  • 10a McBee ET. Kelley AC. Rapkin E. J. Am. Chem. Soc.  1950,  72:  5071 
    CrossrefGoogle Scholar
  • From CF3CH2CH2MgCl and CO2, see:
  • 10b Gavlin G. Maguire RG. J. Org. Chem.  1956,  21:  1342 
    CrossrefGoogle Scholar
  • From CF3CH2CH2CO2Et, see:
  • 10c Walborsky HM. Baum M. Loncrini DF. J. Am. Chem. Soc.  1955,  77:  3637 
    CrossrefGoogle Scholar
  • From CF3CO2Et and CH3CO2Et, see:
  • 10d Raiter M. Pereyere M. Davies AG. Sutcliffe R. J. Chem. Soc., Perkin Trans. 2  1984,  1907 
    CrossrefGoogle Scholar
  • From CF3CH2OTf and malonic ester, see:
  • 10e Tsushima T. Kawada K. Ishihara S. Uchida N. Shiratori O. Higaki J. Hirata M. Tetrahedron  1988,  44:  5375 
    CrossrefGoogle Scholar
  • From C3F7CO2Me and CH3OAc, see:
  • 11a Ahlbrecht AH, and Smith S. inventors; GB  904,263.  ; Chem. Abstr. 1963, 58, 4426
    CrossrefGoogle Scholar
  • From C6F13I and ethyl acrylate (hν), see:
  • 11b Buchanan GW. Smits R. Munteanu E. J. Fluorine Chem.  2003,  123:  255 
    CrossrefGoogle Scholar
  • From C7F15I and ICH=CHI, see:
  • 11c Coe PL. Millner NE. Smith JA. J. Chem. Soc., Perkin Trans. 1  1975,  654 
    CrossrefGoogle Scholar
  • 12 Moore LD. J. Chem. Eng. Data  1964,  9:  251 ; and references cited therein
    CrossrefGoogle Scholar
  • 13a Brace NO. J. Org. Chem.  1962,  27:  3033 
    CrossrefGoogle Scholar
  • 13b Brace NO. inventors; US  3,145,222.  ; Chem. Abstr. 1964, 61, 10589
    Crossref
  • 14 Brace NO. J. Fluorine Chem.  1999,  93:  1 
    CrossrefGoogle Scholar
  • 15a Brace NO. J. Fluorine Chem.  1982,  20:  313 
    CrossrefGoogle Scholar
  • For the addition of (CF3)2CFI to allyl acetate, see:
  • 15b Boggs J, Brandstadter SM, Chien J, Cohn M, Edwards BE, Hedrick V, Jackson A, Leman G, Ameduri B, and Kostov GK. inventors; WO  2005,074,637.  ; Chem. Abstr. 2005, 143, 213355
    CrossrefGoogle Scholar
  • 16a Metzger JO. Mahler R. Schmidt A. Liebigs Ann. Org. Bioorg. Chem.  1996,  5:  693 
    CrossrefGoogle Scholar
  • 16b Vincent J.-M. Rabion A. Yachandra VK. Fish RH. Angew. Chem., Int. Ed. Engl.  1997,  36:  2346 ; Angew. Chem. 1997, 109, 2438
    CrossrefGoogle Scholar
  • 16c Szlávik Z. Tárkányi G. Tarczay Gy. Gömöry Á. Rábai J. J. Fluorine Chem.  1999,  98:  83 
    CrossrefGoogle Scholar
  • 16d Gambaretto G. Conte L. Fornasieri G. Zarantonello C. Tonei D. Sassi A. Bertani R. J. Fluorine Chem.  2003,  121:  57 
    CrossrefGoogle Scholar
  • For replacement of toxic organotin hydrides and/or removal of residual tin compounds from end products, see:
  • 17a Baguley PA. Walton JC. Angew. Chem. Int. Ed.  1998,  37:  3072 ; Angew. Chem. 1998, 110, 3272
    Article in Thieme ConnectGoogle Scholar
  • 17b Studer A. Amrein S. Synthesis  2002,  835 
    Article in Thieme ConnectGoogle Scholar
  • For an improved preparation of 3d and 4d using 1d (100 g) with the triallyl borate/Bu3SnH protocol, see:
  • 17c Rábai J. Kövesi I. Bonto A.-M. In Handbook of Fluorous Chemistry   Gladysz JA. Curran DP. Horváth IT. Wiley-VCH; Weinheim: 2004.  p.419-420  
    Article in Thieme ConnectGoogle Scholar
  • For the use of PtO2/NH4OAc, see:
  • 18a Otsuka T, and Yamamoto S. inventors; JP  2003,146,921.  ; Chem. Abstr. 2003, 138, 385058
    Google Scholar
  • For the use of Pd-C/Et3N, see:
  • 18b Rock M.-H, and Marhold A. inventors; DE  19,748,775.  ; Chem. Abstr. 1999, 130, 268838
    Google Scholar
  • For the use of Raney Ni/KOAc, see:
  • 18c Ukihashi K, and Hayashi T. inventors; JP  7,022,523.  ; Chem. Abstr. 1970, 73, 98363
    Google Scholar
  • For the use of Raney Ni, NaOH, see:
  • 18d Ahlbrecht AH. inventors; US  3,285,975.  ; Chem. Abstr. 1967, 66, 46093
    Google Scholar
  • 19 For hazards with the use of LiAlH4/RF-amides, see: Marks BS. Schweiker GC. J. Am. Chem. Soc.  1958,  80:  5789 
    CrossrefGoogle Scholar
  • 21 Lahiouhel D. Ameduri B. Boutevin B. J. Fluorine Chem.  2001,  107:  81 
    CrossrefGoogle Scholar
  • 22 Daikin Ind. Ltd. . inventors; GB  1,101,049. For an analogous synthesis of 3c with bp 88-90 °C/1.7-2.0 mbar using only 1c, 2, and AIBN at 70-80 °C, see: ; Chem. Abstr. 1968, 68, 60504
  • 23 Bálint A.-M. Bodor A. Gömöry Á. Vékey K. Szabó D. Rábai J. J. Fluorine Chem.  2005,  126:  1524 
    CrossrefGoogle Scholar
7

http://www.fluorous.com.

9

FTI Catalogue (2006) lists RFn(CH2)3OH at $32, $35, $100, and $35 for 2 g each of n = 4, 6, 7, and 8, respectively.

20

Ivanko, P.; Takács, F. T.; Rábai, J. Abstracts of Papers, 14th European Symposium on Fluorine Chemistry, Poznan, Poland, 2004; Abstract 84.