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Synlett 2011(19): 2819-2822  
DOI: 10.1055/s-0031-1289860
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Unique Salt Effect on the High Yield Synthesis of Acid-Labile Terpene Oxides Using Hydrogen Peroxide under Acidic Aqueous Conditions

Houjin Hachiyaa, Yoshihiro Kon*a, Yutaka Onoa, Kiyoshi Takumib, Naoki Sasagawab, Yoichiro Ezakib, Kazuhiko Sato*a
a National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5 Higashi 1-1-1, Tsukuba, Ibaraki 305-8565, Japan
Fax: +81(29)8614670; e-Mail: y-kon@aist.go.jp;
b Arakawa Chemical Industries, Ltd., Tsukuba Okubo 5, Tsukuba, Ibaraki 300-33 Japan
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Publication History

Received 18 August 2011
Publication Date:
09 November 2011 (online)

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Abstract

Acid-labile epoxides such as α-pinene oxide are (effectively) synthesized in high yield from the epoxidation of terpenes with aqueous H2O2 catalyzed by Na2WO4, [Me(n-C8H17)3N]HSO4, and PhP(O)(OH)2 in the presence of Na2SO4 as an auxiliary additive under organic solvent-free conditions at ambient temperature. Origin of the salt effect is considered that the addition of a saturated amount of Na2SO4 to aqueous H2O2 strongly inhibited the undesired hydrolysis of the acid-labile epoxide products, despite the highly acidic reaction conditions.

Key words

oxidation - catalysis - epoxides - terpenoids - green chemistry

    References

  • 1a Ullmann’s Encyclopedia of Industrial Chemistry   5th ed., Vol. A9:  Gerhartz W. Yamamoto YS. Kaudy L. Rounsaville JF. Schulz G. Wiley-VCH; Weinheim: 1987.  p.531 
  • 1b Kirk-Othmer Encyclopedia of Chemical Technology   4th ed., Vol. 9:  Kroschwitz JI. Howe-Grant M. Wiley; New York: 1994.  p.377 
  • 1c Kirk-Othmer Encyclopedia of Chemical Technology   4th ed., Vol. 9:  Kroschwitz JI. Howe-Grant M. Wiley; New York: 1994.  p.730 
  • 2 Larock RC. In Comprehensive Organic Transformations   2nd ed.:  Wiley; New York: 1999.  p.915 
    Search in Google Scholar
  • 3a Strukul G. In Catalytic Oxidations with Hydrogen Peroxide as Oxidant   Kluwer Academic Publishers; Dordrecht: 1992. 
  • 3b Jones CW. In Applications of Hydrogen Peroxide and Derivatives   RSC; Cambridge: 1999. 
  • 4a Trost BM. Science  1991,  254:  1471 
    Search in Google Scholar
  • 4b Sheldon RA. Chem. Ind.  1992,  903 
  • For recent reviews, see:
  • 5a Applied Homogeneous Catalysis with Organometallic Compounds   2nd ed.:  Cornils B. Herrmann WA. Wiley-VCH; Weinheim: 2002. 
  • 5b Lane BS. Burgess K. Chem. Rev.  2003,  103:  2457 
    Search in Google Scholar
  • 5c Grigoropoulou G. Clark JH. Elings JA. Green Chem.  2003,  5:  1 
    Search in Google Scholar
  • 5d Modern Oxidation Methods   Bäckvall J.-E. Wiley-VCH; Weinheim: 2004. 
  • 5e Mizuno N. Yamaguchi K. Kamata K. Coord. Chem. Rev.  2005,  249:  1944 
    Search in Google Scholar
  • 6a Payne GB. Williams PH. J. Org. Chem.  1959,  24:  54 
    Search in Google Scholar
  • 6b Venturello C. Alneri E. Ricci M. J. Org. Chem.  1983,  48:  3831 
    Search in Google Scholar
  • 6c Ishii Y. Yamawaki K. Ura T. Yamada H. Yoshida T. Ogawa M. J. Org. Chem.  1988,  53:  3587 
    Search in Google Scholar
  • 7a Sato K. Aoki M. Ogawa M. Hashimoto T. Noyori R. J. Org. Chem.  1996,  61:  8310 
    Search in Google Scholar
  • 7b Sato K. Aoki M. Ogawa M. Hashimoto T. Panyella D. Noyori R. Bull. Chem. Soc. Jpn.  1997,  70:  905 
    Search in Google Scholar
  • 7c Noyori R. Aoki M. Sato K. Chem. Commun.  2003,  1977 
  • 8a Sienel G. Rieth R. In Ullmann’s Encyclopedia of Industrial Chemistry   6th ed., Vol. 12:  Wiley-VCH; Weinheim: 2003.  p.279 
    Search in Google Scholar
  • 8b Eggersdorfer M. In Ullmann’s Encyclopedia of Industrial Chemistry   6th ed., Vol. 35:  Wiley-VCH; Weinheim: 2003.  p.653 
    Search in Google Scholar
  • 8c Swift KAD. Top. Catal.  2004,  27:  143 
    Search in Google Scholar
  • 8d Corma A. Iborra S. Velty A. Chem. Rev.  2007,  107:  2411 
    Search in Google Scholar
  • 8e Bicas JL. Dionísio AP. Pastore GM. Chem. Rev.  2009,  109:  4518 
    Search in Google Scholar
  • 9a Kon Y. Ono Y. Matsumoto T. Sato K. Synlett  2009,  1095 
  • 9b Kon Y. Hachiya H. Ono Y. Matsumoto T. Sato K. Synthesis  2011,  1092 
  • 10a Hou S.-Y. Zhou Z.-H. Lin T.-R. Wan H.-L. Eur. J. Inorg. Chem.  2006,  1670 
  • 10b Maheswari PU. Tang X. Hage R. Gamez P. Reedijk J. J. Mol. Catal. A: Chem.  2006,  258:  295 
    Search in Google Scholar
  • 11 Kolehmainen E. Laihia K. Heinänen M. Rissanen K. Fröhlich R. Korvola J. Mänttäri P. Kauppinen R.
    J. Chem. Soc., Perkin Trans. 2  1993,  641 
  • 12a Kopperman HL. Hallcher RCSr. Riehl A. Carlson RM. Caple R. Tetrahedron  1976,  32:  1621 
    Search in Google Scholar
  • 12b Liu W. Rosazza JPN. Synth. Commun.  1996,  26:  2731 
    Search in Google Scholar
  • 13 Grigoropoulou G. Clark JH. Tetrahedron Lett.  2006,  47:  4461 
    Search in Google Scholar
  • 14a McDevit WF. Long FA. J. Am. Chem. Soc.  1952,  74:  1773 
    Search in Google Scholar
  • 14b Long FA. McDevit WF. Chem. Rev.  1952,  51:  119 
    Search in Google Scholar
  • 15 Hofmeister F. Arch. Exp. Pathol. Pharmacol.  1887,  24:  247 
    Search in Google Scholar
  • 16a Poulson SR. Harrington RR. Drever JI. Talanta  1999,  48:  633 
    Search in Google Scholar
  • 16b Görgényi M. Dewulf J. Langenhove HV. Héberger K. Chemosphere  2006,  65:  802 
    Search in Google Scholar