Diastereoselective Rhodium-Catalyzed Ene-Cycloisomerization Reactions of Alkenylidenecyclopropanes: Total Synthesis of (-)-α-Kainic Acid

被引：67

作者：

Evans, P. Andrew ^{[1
]}

Inglesby, Phillip A. ^{[1
]}

机构：

[1] Univ Liverpool, Dept Chem, Liverpool L69 7ZD, Merseyside, England

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 08期

基金：

英国工程与自然科学研究理事会;

关键词：

SIGMATROPIC REARRANGEMENTS; ENANTIOSELECTIVE SYNTHESIS; (+)-ALPHA-ALLOKAINIC ACID; ASYMMETRIC-SYNTHESIS; CYCLIZATION; METAL; CYCLOADDITION; ISOMERIZATION; 1,6-DIENES; N-ENYNES;

D O I：

10.1021/ja210804r

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The rhodium-catalyzed ene-cycloisomerization of alkenylidenecyclopropanes provides an atom-economical approach to five-membered carbo- and heterocycles that contain two new stereogenic centers. A Me key and striking feature of this protocol is that the alkene geometry does not impact the efficiency and diastereocontrol, which provides excellent synthetic versatility. For instance, (E)- and (Z)-allylic alcohols furnish the corresponding aldehydes with similar efficiency and selectivity. This process facilitates the construction of a key intermediate in an eight-step total synthesis of (-)-alpha-kainic acid.

引用

页码：3635 / 3638

页数：4

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