An Organometallic Approach to Peroxyketals

Patrick H Dussault, Ayman Sahli, Thane Westermeyer

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

A new method for peroxyketal synthesis is presented based upon formation of carbon-carbon bonds in the presence of a protected hydroperoxide. The 2-methoxypropyl perketal of 4(S)-hydroperoxy-2(E)-nonenal (2) undergoes reaction with a variety of metal hydrides and organometallic reagents to produce 4-peroxy 2-enols in good to excellent yields via chemoselective addition to the carbonyl carbon. Oxidation of the allylic alcohol to the 4-peroxy 2-enone is followed by deprotection to furnish a single enantiomer of a 4-hydroxyperoxy 2(E)-enone. Photochemical isomerization by the method of Snider induces spontaneous cyclization to epimeric 3-hydroxy-1,2-dioxins (hydroxy endoperoxides). Acidic methanolysis furnishes readily separable diastereomeric perketals as single enantiomers.

Original languageEnglish (US)
Pages (from-to)5469-5474
Number of pages6
JournalJournal of Organic Chemistry
Volume58
Issue number20
DOIs
StatePublished - Jan 1 1993

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Organometallics
Carbon
Enantiomers
Dioxins
Cyclization
Isomerization
Hydrides
Hydrogen Peroxide
Metals
Oxidation

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

An Organometallic Approach to Peroxyketals. / Dussault, Patrick H; Sahli, Ayman; Westermeyer, Thane.

In: Journal of Organic Chemistry, Vol. 58, No. 20, 01.01.1993, p. 5469-5474.

Research output: Contribution to journalArticle

Dussault, Patrick H ; Sahli, Ayman ; Westermeyer, Thane. / An Organometallic Approach to Peroxyketals. In: Journal of Organic Chemistry. 1993 ; Vol. 58, No. 20. pp. 5469-5474.
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