Peroxycarbenium-mediated C-C bond formation

Applications to the synthesis of hydroperoxides and peroxides

Patrick H Dussault, In Quen Lee, H. J. Lee, R. J. Lee, Q. J. Niu, J. A. Schultz, U. R. Zope

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

The Lewis acid-mediated reaction of alkene nucleophiles with peroxyacetals provides an effective route for the synthesis of homologated peroxides and hydroperoxides. In the presence of Lewis acids such as TiCl4, SnCl4, and trimethylsilyl triflate, peroxyacetals and peroxyketals undergo reaction with allyltrimethylsilane, silyl enol ethers, and silyl ketene acetals to afford homoallyl peroxides, 3-peroxyketones, and 3-peroxyalkanoates, respectively. Reactions of peroxyacetals are Lewis acid dependent; TiCl4 promotes formation of ethers while SnCl4 and trimethylsilyl triflate promote formation of peroxides. Lewis acid-promoted reactions of silylated hydroperoxyacetals furnish silylated hydroperoxides, which can be deprotected to homologated hydroperoxides. Hydroperoxyketals undergo Lewis acid-mediated allylation to furnish 1,2-dioxolanes via attack of hydroperoxide on the intermediate carbocation. Lewis acid-mediated cyclization of unsaturated peroxyacetals furnishes 1,2-dioxanes, 1,2-dioxepanes, and 1,2-dioxacanes through 6-endo/exo, 7-endo/endo, and 8-endo/endo pathways. The corresponding reactions involving 6-endo/endo and 5-endo/exo pathways were unsuccessful.

Original languageEnglish (US)
Pages (from-to)8407-8414
Number of pages8
JournalJournal of Organic Chemistry
Volume65
Issue number25
DOIs
StatePublished - Dec 15 2000

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Lewis Acids
Peroxides
Hydrogen Peroxide
Ethers
Dioxanes
Dioxolanes
Allylation
Acetals
Nucleophiles
Cyclization
Alkenes

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Peroxycarbenium-mediated C-C bond formation : Applications to the synthesis of hydroperoxides and peroxides. / Dussault, Patrick H; Lee, In Quen; Lee, H. J.; Lee, R. J.; Niu, Q. J.; Schultz, J. A.; Zope, U. R.

In: Journal of Organic Chemistry, Vol. 65, No. 25, 15.12.2000, p. 8407-8414.

Research output: Contribution to journalArticle

Dussault, Patrick H ; Lee, In Quen ; Lee, H. J. ; Lee, R. J. ; Niu, Q. J. ; Schultz, J. A. ; Zope, U. R. / Peroxycarbenium-mediated C-C bond formation : Applications to the synthesis of hydroperoxides and peroxides. In: Journal of Organic Chemistry. 2000 ; Vol. 65, No. 25. pp. 8407-8414.
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