The C-ring problem of sterol biosynthesis:: TiCl4-induced rearrangement into the anti-Markovnikov cation corresponding to the C-ring

被引：12

作者：

Nishizawa, M ^{[1
]}

Iwamoto, Y ^{[1
]}

Takao, H ^{[1
]}

Imagawa, H ^{[1
]}

Sugihara, T ^{[1
]}

机构：

[1] Tokushima Bunri Univ, Fac Pharmaceut Sci, Yamashiro, Tokushima 7708514, Japan

来源：

ORGANIC LETTERS | 2000年 / 2卷 / 12期

关键词：

D O I：

10.1021/ol0057582

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] Cation 9, generated by the reaction of diol 8 and BF3-Et2O, SnCl4, Sc(OTf)(3), FeCl3, TiF4, or CF3SO3H, leads to a hydride shift, providing cation 11, which corresponds to the initiation of backbone rearrangement. On the other hand, TiCl4 selectively induces rearrangement to secondary cation 13 by ring expansion, which corresponds to the C-ring formation of sterol biosynthesis. AlCl3 and ZrCl4 induce further rearrangement into six-membered ring tert-cation 16.

引用

页码：1685 / 1687

页数：3

共 31 条

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