Peroxycarbenium-mediated C-C bond formation: Applications to the synthesis of hydroperoxides and peroxides

被引：56

作者：

Dussault, PH ^{[1
]}

Lee, IQ ^{[1
]}

Lee, HJ ^{[1
]}

Lee, RJ ^{[1
]}

Niu, QJ ^{[1
]}

Schultz, JA ^{[1
]}

Zope, UR ^{[1
]}

机构：

[1] Univ Nebraska, Dept Chem, Lincoln, NE 68588 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2000年 / 65卷 / 25期

关键词：

D O I：

10.1021/jo991714z

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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.

引用

页码：8407 / 8414

页数：8

共 63 条

[11] OBSERVATIONS ON THE SCOPE OF AN INTRAMOLECULAR DIRECTED ALDOL CONDENSATION - A NEW SYNTHESIS OF 8-MEMBERED RINGS [J].