Download PDF
Synthesis 2008(10): 1641-1645  
DOI: 10.1055/s-2008-1032161
PSP
© Georg Thieme Verlag Stuttgart · New York

Partial Oxidation of Alkenylsilanes with Ozone: A Novel Stereoselective Approach to the Diol and Triol Derivatives

Kazunobu Igawaa, Kyohei Sakitab, Masanori Murakamib, Katsuhiko Tomooka*a,b
a Institute for Materials Chemistry and Engineering, Kyushu University, Kasuga-koen 6-1, Kasuga-shi, Fukuoka 816-8580, Japan
Fax: +81(92)5837810; e-Mail: ktomooka@cm.kyushu-u.ac.jp;
b Department of Applied Chemistry, Tokyo Institute of Technology, Ookayama 2-12-1, Meguro-ku, Tokyo 152-8552, Japan
Further Information

Publication History

Received 22 October 2007
Publication Date:
08 February 2008 (online)

    Permissions and Reprints All articles of this category

Abstract

The reaction of alkenylsilanes with ozone provides synthetically versatile β-hydroxy or α-formyl silyl peroxides in good yield without normal fission of the C=C bond. The obtained α-formyl silyl peroxides serve as good precursors for the stereochemically defined diol or triol derivatives via nucleophilic addition to the formyl group and reduction of the peroxide moiety.

Key words

alkenes - oxidations - ozonolysis - peroxides - silicon

    References

  • For leading reviews on ozonolysis and other ozone oxidations, see:
  • 1a Bailey PS. Ozonation in Organic Chemistry, Olefinic Compounds   Vol. 1:  Academic Press; London: 1978. 
    Google Scholar
  • 1b Bailey PS. Ozonation in Organic Chemistry, Nonolefinic Compounds   Vol. 2:  Academic Press; London: 1982. 
    Google Scholar
  • 2 Theoretical studies suggest that the formation of primary ozonide is a rate-determining step for the ozonolysis of alkenes. For a representative example, see: Anglada MJ. Crehuet R. Bofill JM. Chem. Eur. J.  1999,  5:  1809 
    CrossrefGoogle Scholar
  • 3 Murakami M. Sakita K. Igawa K. Tomooka K. Org. Lett.  2006,  8:  4023 
    CrossrefGoogle Scholar
  • 4 Büchi and Wüest reported the ozonization of trimethylsilyl-substituted alkenes in the 1970s, in which they proposed a similar silyl peroxide as an intermediate, see: Büchi G. Wüest H. J. Am. Chem. Soc.  1978,  100:  294 
    CrossrefGoogle Scholar
  • 6a Castrantas HM. Banerjee DK. Noller DC. Fire and Explosion Hazards of Peroxy Compounds, ASTM STP 394   American Society for Testing and Materials; Philadelphia PA: 1965. 
    Google Scholar
  • 6b Castrantas HM. Banerjee DK. Laboratory Handling and Storage of Peroxy Compounds, ASTM STP 471   American Society for Testing and Materials; Philadelphia PA: 1970. 
    Google Scholar
  • 8a Denmark SE. Jones TK. J. Org. Chem.  1982,  47:  4595 
    CrossrefGoogle Scholar
  • 8b Igawa K. Tomooka K. Angew. Chem. Int. Ed.  2006,  45:  232 
    CrossrefGoogle Scholar
  • 9 A related reduction of silyl peroxide in a norcamphor derivative has been reported, see: Jefford CW. Rimbault CG. J. Am. Chem. Soc.  1978,  100:  6437 
    CrossrefGoogle Scholar
  • 10 Cyclic peroxide has been utilized as a synthetic equivalent of ketone, see: Singh C. Malik H. Org. Lett.  2005,  7:  5673 
    CrossrefPubMedGoogle Scholar
5

Normal oxidative cleavage products were obtained in the ozonation of alkenylsilanes 1 in MeOH, CH2Cl2 or hexane in 10-30% yields.

7

Although Büchi’s trimethylsilyl peroxide is too reactive to be handled with ease (see ref. 4), our silyl peroxides are tolerant not only to the reductive workup process using NaBH4 but also to purification on silica gel, most probably due to the bulky silyl group on the peroxide moiety. Furthermore, slow thermal degradation was observed at >80 °C in thermogravimetric analysis (TGA) of 2c and 4q; see ref. 3.