Highly functionalized cyclohexenyl systems:: Enzymatic resolution and selective oxirane opening reactions of p-benzoquinone derivatives

被引：15

作者：

Kohrt, JT ^{[1
]}

Gu, JX ^{[1
]}

Johnson, CR ^{[1
]}

机构：

[1] Wayne State Univ, Dept Chem, Detroit, MI 48202 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1998年 / 63卷 / 15期

关键词：

D O I：

10.1021/jo980270o

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Diol 2, derived in two steps from p-benzoquinone, was converted to epoxy alcohol 3. The latter was resolved with crude Candida rugosa lipase in isopropenyl acetate/toluene to give acetate (-)-4 and residual alcohol (+)-3. Oxirane ring opening reactions of 3 and the corresponding acetate and TBDMS derivatives with a variety of nucleophiles gave diastereomerically pure 3,4,5,6-tetrasubstituted cyclohexene derivatives of type 6. X-ray crystal structures were obtained on compounds 6e, 6m and the diacetate prepared from 6l. Nitrogen nucleophiles provided entry in various aziridines 10. Pd(0)-catalyzed nucleophilic additions to substrate 5 cleanly provided the diastereomeric pattern of type 11. trans-5,6-Disubstituted cyclohexadienes 13 were obtained by an unusual syn-reductive elimination on bromocarbonates 12 utilizing Pd or Zn.

引用

页码：5088 / 5093

页数：6

共 45 条

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