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Synthesis 2008(15): 2373-2380  
DOI: 10.1055/s-2008-1067169
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Facile Syntheses of Symmetrical Diaryliodonium Salts from Various Arenes, with Sodium Metaperiodate as the Coupling Reagent in Acidic Media [¹]

Lukasz Kraszkiewicz, Lech Skulski*
Chair and Laboratory of Organic Chemistry, Faculty of Pharmacy, Medical University, 1 Banacha Street, 02-097 Warsaw, Poland
Fax: +48(22)5720643.; e-Mail: lechskulski@yahoo.com.;
Further Information

Publication History

Received 18 March 2008
Publication Date:
08 July 2008 (online)

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Abstract

An easy, inexpensive, safe, and effective preparative procedure to obtain symmetrical diaryliodonium bromides (in 17-88% crude yields) from various arenes is presented in this paper. A novel method for the in situ preparation of iodosyl sulfate (Chrétien’s reagent) is given. Eleven exemplary crude diaryliodonium bromides were readily oxidatively metathesized with 40% aqueous tetrafluoroboric acid and 30% aqueous hydrogen peroxide (in boiling acetone, used both as a solvent and ‘halogen scavenger’) to give pure diaryliodonium tetrafluoroborates in 15-85% yields.

Key words

symmetrical diaryliodonium salts - arenes - sodium metaperiodate - iodosyl sulfate - oxidative anion metatheses

    References

  • 1 These results were presented in part at the 9th International Electronic Conference on Synthetic Organic Chemistry (ECSOC-9), November 1-30th, 2005; Paper A022; see http://www.usc.es/congresos/ecsoc/9/ECSOC9.HTM and Chem. Abstr.  2007,  147:  30753 
    Google Scholar
  • For reviews on aromatic iodonium salts, see:
  • 2a Olah GA. Halonium Ions   Wiley; New York: 1975. 
    Google Scholar
  • 2b Koser GF. In The Chemistry of Functional Groups, Suppl. D   Patai S. Rappoport Z. Wiley; Chichester: 1983.  Chap. 25.
    Google Scholar
  • 2c Varvoglis A. The Organic Chemistry of Polycoordinated Iodine   VCH; Weinheim: 1992. 
    Google Scholar
  • 2d Koser GF. In The Chemistry of Halides, Pseudo-Halides and Azides, Suppl. D2   Patai S. Rappoport Z. Wiley-Interscience; Chichester: 1995.  Chap. 21.
    Google Scholar
  • 2e Stang PJ. Zhdankin VV. Chem. Rev.  1996,  96:  1123 
    Google Scholar
  • 2f Varvoglis A. Hypervalent Iodine in Organic Synthesis   Academic Press; San Diego: 1997. 
    Google Scholar
  • 2g Chemistry of Hypervalent Compounds   Akiba K. Wiley-VCH; New York: 1999.  Chap. 11 and 12.
    Google Scholar
  • 2h Zhdankin V. V., Stang P. J.; Chem. Rev.; 2002, 102: 2523
    Google Scholar
  • 2i Hypervalent Iodine Chemistry, In Topics in Current Chemistry   Vol. 224:  Wirth T. Springer; Berlin: 2003. 
    Google Scholar
  • 2j Stang PJ. J. Org. Chem.  2003,  68:  2997 
    Google Scholar
  • 3 van der Puy M. J. Fluorine Chem.  1982,  21:  385 
    CrossrefGoogle Scholar
  • 4 Sandin RB. Chem. Rev.  1943,  32:  249 ; see p 266
    CrossrefGoogle Scholar
  • 5 Hickey DMB. Lesson PD. Novelli R. Shah VP. Burpitt BE. Crawford LP. Davies BJ. Mitchell MB. Pancholi KD. Tuddenham D. Lewis NJ. O’Farrell C. J. Chem. Soc., Perkin Trans. 1  1988,  3103 ; see Table 2 therein and its explanation on p 3106
    CrossrefGoogle Scholar
  • 6 Beringer FM. Falk RA. Karniol M. Lillien I. Masullo G. Mausner M. Sommer E. J. Am. Chem. Soc.  1959,  81:  342 
    CrossrefGoogle Scholar
  • 7a Hossain D. Ikegami Y. Kitamura T. J. Org. Chem.  2006,  71:  9903 ; which gives references in the literature to all previous methods for the preparation of diaryliodonium triflates
    Google Scholar
  • 7b Hossain D. Kitamura T. Bull. Chem. Soc. Jpn.  2007,  80:  2213 
    Google Scholar
  • 8 For a review in Polish, see: Krassowska-Swiebodzka B. Rudzki P. Biul. Wydz. Farm. AMW  2004,  1 ; http://www.farm.amwaw.edu.pl/˜axzimni/biuletyn/0401Krassowska/Ojodylar.html
    Google Scholar
  • 9a Beringer FM. Nathan RA. J. Org. Chem.  1969,  34:  685 
    Google Scholar
  • 9b Beringer FM. Nathan RA. J. Org. Chem.  1970,  35:  2095 
    Google Scholar
  • 9c Gronowitz S. Holm B. Synth. Commun.  1974,  4:  63 
    Google Scholar
  • 11 Cornforth J. Ridley DD. Sierakowski AF. Uguen D. Wallace TW. Hitchcock PB. J. Chem. Soc., Perkin Trans. 1  1982,  2317 
    CrossrefGoogle Scholar
  • 12 Tyrra W. Butler H. Naumann D. J. Fluorine Chem.  1993,  60:  79 
    CrossrefGoogle Scholar
  • 13a Lulinski P. Skulski L. Bull. Chem. Soc. Jpn.  2000,  73:  951 
    Google Scholar
  • 13b Kraszkiewicz L. Sosnowski M. Skulski L. Tetrahedron  2004,  60:  9113 
    Google Scholar
  • 13c Kraszkiewicz L. Sosnowski M. Skulski L. Synthesis  2006,  1195 
    Google Scholar
  • 14 Lulinski P. Sosnowski M. Skulski L. Molecules  2005,  10:  516 ; http://www.mdpi.org/molecules/papers/10030516.pdf
    CrossrefPubMedGoogle Scholar
  • 15 Kasumov TM. Koz‘min AS. Zefirov NS. Russ. Chem. Rev.  1997,  66:  843 ; Usp. Khim. 1997, 66, 936
    CrossrefGoogle Scholar
  • 16a Chrétien MP. Ann. Chim. Phys.  1898,  15:  358 
    Google Scholar
  • 16b All former methods for preparing iodosyl sulfate are related in ref 15, p 942, as well as in the earlier paper: Masson I. Argument C. J. Chem. Soc.  1938,  1702 
    Google Scholar
  • 16c Concerning Scheme 9: for more information on hygroscopic and easily hydrolyzable iodylbenzene sulfate, PhIO2˙H2SO4 (mp 127 ˚C), see: Masson I. Race E. Pounder FE. J. Chem. Soc.  1935,  1669 
    Google Scholar
  • 17a Beringer FM. Briedley A. Drexler M. Gindler EM. Lumpkin CC. J. Am. Chem. Soc.  1953,  75:  2708 
    Google Scholar
  • 17b Beringer FM. Falk RA. J. Chem. Soc.  1964,  4442 
    Google Scholar
  • 17c Caserio MC. Glusker DL. Roberts JD. J. Am. Chem. Soc.  1959,  81:  336 
    Google Scholar
  • 18a Kazmierczak P. Skulski L. Synthesis  1995,  1027 
    Google Scholar
  • 18b Kazmierczak P. Skulski L. Bull. Chem. Soc. Jpn.  1997,  70:  219 
    Google Scholar
  • 19 Skulski L. Molecules  2000,  5:  1331 ; http://www.mdpi.org/molecules/papers/51201331.pdf
    CrossrefGoogle Scholar
  • 20 Kryska A. Skulski L. Molecules  2001,  6:  875 ; http://www.mdpi.org/molecules/papers/61100875.pdf
    CrossrefGoogle Scholar
  • 21a Lulinski P. Ph.D. Thesis   Warsaw Medical University; Poland: 2002. 
    Google Scholar
  • 21b Sosnowski M. Ph.D. Thesis   Warsaw Medical University; Poland: 2005. 
    Google Scholar
  • 21c Zielinska A. Ph.D. Thesis   Warsaw Medical University; Poland: 2006. 
    Google Scholar
  • 21d

    Kraszkiewicz, L. Ph.D. Thesis, Warsaw Medical University: Poland, in preparation.

  • 22 Forster MO. Schaeppi JH. J. Chem. Soc.  1912,  101:  382 
    CrossrefGoogle Scholar
  • 23 Beringer FM. Dehn JW. Winicov M. J. Am. Chem. Soc.  1960,  82:  2948 
    CrossrefGoogle Scholar
  • 24 McRae J. Ber. Dtsch. Chem. Ges.  1895,  28:  97 
    CrossrefGoogle Scholar
  • 25 Willgerodt C. J. Prakt. Chem.  1900,  61:  424 
    Google Scholar
  • 26 Beringer FM. Gindler EM. Iodine Abstr. Rev.  1956,  3:  70 
    Google Scholar
  • 27 Lyatiev GG. Ptitsyna OA. Reutov OA. J. Org. Chem. USSR  1969,  5:  400 ; Zh. Org. Khim. 1969, 5, 411
    Google Scholar
  • 28 Reutov OA. Ertel G. Ptizyna OA. Chem. Ber.  1960,  93:  2613 
    CrossrefGoogle Scholar
  • 29 Farhan AN. Kryska A. Skulski L. Bull. Pol. Acad. Sci., Chem.  1996,  44:  201 
    Google Scholar
  • 30 Zhu M. Jalalian N. Olofsson B. Synlett  2008,  592 
    Article in Thieme ConnectGoogle Scholar
10

Frohn, H. J. unpublished results related in ref 2c, pp 215-217.