AN ORGANOMETALLIC APPROACH TO PEROXYKETALS
AN ORGANOMETALLIC APPROACH TO PEROXYKETALS
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DOI：
10.1021/jo00072a032
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发表时间：
1993-09-24
影响因子：
3.6
通讯作者：
WESTERMEYER, T
中科院分区：
文献类型：
--
作者：
DUSSAULT, P;SAHLI, A;WESTERMEYER, T
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.
