Tandem use of cobalt-mediated reactions to synthesize (+)-epoxydictymene, a diterpene containing a trans-fused 5-5 ring system

被引：144

作者：

Jamison, TF ^{[1
]}

Shambayati, S ^{[1
]}

Crowe, WE ^{[1
]}

Schreiber, SL ^{[1
]}

机构：

[1] HARVARD UNIV,HOWARD HUGHES MED INST,DEPT CHEM & CHEM BIOL,CAMBRIDGE,MA 02138

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1997年 / 119卷 / 19期

关键词：

D O I：

10.1021/ja970022u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The diterpene (+)-epoxydictymene has been synthesized in 20 steps using the asymmetry of (R)-pulegone and several substrate-controlled diastereoselective reactions to prepare the natural product in its natural configuration. Three of the four rings were assembled with two consecutive intramolecular reactions involving dicobalt hexacarbonyl complexes of alkynes: a Lewis acid-promoted Nicholas reaction and a Pauson-Khand reaction. The construction of the strained trans-3-oxabicyclo[3.3.0]octane ring system of the natural product presented a significant challenge. To this end, several radical and anionic cyclizations were studied, the latter leading to (+)-epoxydictymene.

引用

页码：4353 / 4363

页数：11

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